D. Muller, A. Alexakis
"Rhodium and Copper-catalyzed asymmetric conjugate addition of alkenyl nucleophiles"
Chem. Commun.2012, 48, 12037-12049.
Since the initial reports in the mid 90s, metal catalyzed asymmetric conjugate addition (ACA) reactions evolved as an important tool for the synthetic chemist. Most of the research efforts have been done in the field of rhodium and copper catalyzed ACA reactions employing aryl and alkyl nucleophiles. Despite the great synthetic value of the double bond, the addition of alkenyl nucleophiles remains insufficiently explored. In this account, an overview of the developments in the field of rhodium and copper catalyzed ACA reactions with organometallic alkenyl reagents (B,Mg, Al, Si, Zr, Sn) will be provided. The account is intended to give a comprehensive overview of all the existing methods. However, in many cases only selected examples are displayed in order to facilitate comparison of different ligands and methodologies.
D. Grassi, H. Li, A. Alexakis
"Formation of chiral fluoroalkyl products through copper-free enantioselective allylic alkylation catalyzed by an NHC ligand"
Chem. Commun.2012, 48, 11404-11406.
A valuable Cu-free protocol is reported where NHC ligand has been employed to form quaternary centers bearing fluoroalkyl unities. Importantly the results obtained, from this allylic substitution, are better in terms of enantioselectivity and regioselectivity compared to the copper catalyzed system. Moreover the catalysis is performed directly on the substrate containing the fluoroalkyl moiety. The use of FSBM as fluoromethide equivalent is not anymore required. The reaction has been extended to CF2H group (isosteric to carbinol function) and to CF3 group.
F. Romanov-Michailidis, C. Besnard, A. Alexakis
"N-Heterocyclic Carbene-Catalyzed Annulation of α-Cyano-1,4-diketones with Ynals"
Org. Lett.2012, 14, 4906-4909.
In this paper, the first stereoselective annulation reaction between α-cyano-1,4-diketones and ynals, mediated by catalytic amounts of a triazolium salt precatalyst and cocatalytic amounts of a weak carboxylate base, is disclosed. The title transformation proceeds smoothly under mild reaction conditions and generates three contiguous stereogenic centers, one of which is a quaternary acetal carbon. This reaction tolerates a wide variety of electronically distinct substituents on both reaction partners and affords privileged bicyclic scaffolds in 61–90% isolated yields and with up to 20:1 diastereomeric preference.
N. Germain, M. Magrez, S. Kehrli, M. Mauduit, A. Alexakis
"Chiral NHC Ligands for the Copper-Catalyzed Asymmetric Conjugate Addition of Grignard Reagents"
Eur. J. Org. Chem.2012, 5301-5306.
In this paper, we disclose our recent advances in the copper-catalyzed enantioselective conjugate addition of Grignard reagents to 3-substituted cyclic enones. Several new N-heterocyclic carbene (NHC) ligands have been synthesized in high yields by starting from inexpensive materials. These new NHCs were evaluated as ligands for copper, for the Michaeladdition of ethylmagnesium bromide leading to chiral 3,3-disubstituted cyclohexanones (up to 93 % ee). The best ligand was then engaged in conjugate additions of various Grignard reagents, allowing the formation of quaternary centers with high levels of regio- and enantioselectivity with only 0.75 mol-% catalyst loading. The reaction is also robust to scale-up. The addition of ethylmagnesium bromide for the construction of a 3,3-disubstituted cyclopentanone (up to 86 % ee), a synthetically useful chiral synthon, is noteworthy. A tentative mechanism for the catalytic cycle is also discussed.
M. Magrez, J. Wencel-Delord, A. Alexakis, C. Crévisy, M. Mauduit
"Significant Asymmetric Amplification in Enantioselective Cu/DiPPAM-catalyzed 1,6- and 1,4-Conjugate Additions of Diethylzinc to (Di)enones"
Org. Lett.2012, 14, 3576-3579.
An unprecedented and strong positive nonlinear effect (NLE) was observed in Cu/DiPPAM-catalyzed asymmetric 1,6-conjugate addition of Et2Zn on (E)-3-(prop-1-en-1-yl)cyclohex-2-enone (71% ee reached with a 40% ee ligand). Moreover, similar behaviors were observed in Cu/DiPPAM-catalyzed 1,4-asymmetric conjugate additions of Et2Zn on both cyclohexenone and (E)-3-non-3-en-2-one (83% and 70% ee, respectively, reached with a 40% ee ligand).
M. Tissot, D. Poggiali, H. Hénon, D. Müller, L. Guénée, M. Mauduit, A. Alexakis
"Formation of Quaternary Stereogenic Centers by NHC–Cu-Catalyzed Asymmetric Conjugate Addition Reactions with Grignard Reagents on Polyconjugated Cyclic Enones"
Chem. Eur. J.2012, 18, 8731-8747.
The copper-catalyzed conjugate addition of various Grignard reagents to polyconjugated enones (dienone and enynone derivatives) is reported. The catalyst system, composed of copper triflate and an NHC ligand, led to the unusual selective formation of the 1,4-addition products. This reaction allows for the creation of all-carbon chiral quaternary centers with enantiomeric excesses up to 99 %. The remaining unsaturation on the 1,4 adducts give access to valuable synthetic transformations.
J. Praz, L. Guénée, S. Aziz, A. Berkessel, A. Alexakis
"Evaluation of the Chiral DIANANE Backbone as Ligand for Organolithium Reagents"
Adv. Synth. Catal.2012, 354, 1780-1790.
Novel endo,endo-2,5-diaminonorbonanederived tertiary C2-symmetrical diamines were synthesized via the one-pot reductive amination of enantiomerically pure norbornane-2,5-dione. These ligands were applied to various catalytic reactions such as asymmetric deprotonation, asymmetric bromine-lithium exchange, and enantioselective addition of aryl- and allkylithium reagents to aromatic aldimines.
L. Gremaud, L. Palais, A. Alexakis
"Copper-catalyzed Asymmetric Conjugate Addition to Challenging Michael Acceptors and Synthesis of Relevant Target Molecules"
CHIMIA2012, 66, 196-200.
We report herein the enantioselective Cu-catalyzed conjugate addition of organometallic reagents to sensitive Michael acceptors and their application to the synthesis of relevant target molecules. This is one of the most important methodologies to form a C–C bond in an enantioselective manner. A wide range of α,β-unsaturated aldehydes and β,γ-unsaturated-α-ketoesters has been successfully used. Reactivity, regioand enantioselectivities were strongly dependent on the reaction conditions, therefore moderate to very good results were obtained. Furthermore, γ-substituted-α-ketoesters were used as chiral building blocks for further derivatization with complete retention of the chiral information to obtain key compounds.
D. Müller, A. Alexakis
"Copper-Catalyzed Asymmetric 1,4-Addition of Alkenyl Alanes to N-Substituted-2-3-dehydro-4-piperidones"
Org. Lett.2012, 14, 1842-1845.
Readily available vinyl alanes are used in the Cu-catalyzed asymmetric conjugate addition reaction to N-substituted-2-3-dehydro-4-piperidones. The enhanced reactivity of recently developed and easily prepared phosphine amine ligands in combination with inexpensive Cu(II)naphtenate (CuNp) allows the introduction of a great variety of alkenyl, alkyl, and aryl aluminums in high enantioselectivity.
D. Grassi, A. Alexakis
"Copper-Free Asymmetric Allylic Alkylation Using Grignard Reagents on Bifunctional Allylic Bromides"
Org. Lett.2012, 14, 1568-1571.
A series of substrates containing a vinylic bromide were employed in a copper-free methodology using bidendate NHC ligands. The desired compounds are generally obtained with good enantioselectivity and good regioselectivity. Importantly the copper-catalyzed system afforded a lower enantioselectivity value. The catalytic products could be transformed into a broad scope of new 1,1-disubstituted olefins in a single step transformation without erosion of the enantioselectivity.
M. Magre, J. Mazuela, M. Diéguez, O. Pàmies, A. Alexakis
"Furanoside phosphite–phosphoroamidite and diphosphoroamidite ligands applied to asymmetric Cu-catalyzed allylic substitution reactions"
Tetrahedron: Asymmetry2012, 23, 67-71.
A phosphite-phosphoroamidite and diphosphoroamidite ligand library was applied in the Cu-catalyzed allylic substitution of a range of cinnamyl-type substrates using several organometallic nucleophiles. Results indicated that selectivity depended strongly on the ligand parameters (position of the phosphoroamidite group at either C-5 or C-3 of the furanoside backbone, as well as the configuration of C-3, the introduction of a second phosphoroamidite moiety, the substituents and configurations in the biaryl phosphite/phosphoroamidite moieties), the nature of the leaving group of the substrate and the alkylating reagent. Good enantioselectivities (up to 76%) and activity combined with high regioselectivities were obtained.
J.-B. Langlois, D. Emery, J. Mareda, A. Alexakis
"Mechanistic identification and improvement of a direct enantioconvergent transformation in copper-catalyzed asymmetric allylic alkylation"
Chem. Sci.2012, 3, 1062-1069.
Recently, our group reported on the development of an unprecedented process in copper-catalyzed Asymmetric Allylic Alkylation. This method allowed for the quantitative transformation of a racemic substrate into an enantioenriched product. While a high level of asymmetric induction (up to 99% ee) was observed, the mechanistic understanding of the reaction remained fuzzy. In the present article, a thorough mechanistic analysis, based on computational investigations, led to the identification of the reaction pathway. Notably, it uncovered that both enantiomers of the starting material converged independently to the same product via two different mechanistic routes. This specific feature established this process as a rare example of Direct Enantioconvergent Transformation. Finally, the modelling results prompted a valuable improvement of the reaction, relying on the use of a more accessible range of substrates.
A select few: Several prochiral enyne chlorides were employed as substrates in the title reaction using Grignard reagents as the alkylation reagents (see scheme; CuTC=copper(I) thiophenecarboxylate). Excellent 1,3 substitution regioselectivities and good to excellent enantioselectivities were obtained. The substrate scope is additionally extended to diene chlorides.
L. Gremaud, A. Alexakis
"Enantioselective Copper-Catalyzed Conjugate Addition of Trimethylaluminium to β,γ-Unsaturated α-Ketoesters"
Angew. Chem. Int. Ed.2012, 51, 794-797.
Not a cop out: The copper-catalyzed asymmetric conjugate addition of organometallic reagents to Michael acceptors is an important methodology for forming a C—C bond in an enantioselective manner. Such an addition of Me3Al to β,γ-unsaturated α-ketoesters is described to proceed in high yield and selectivity. CuTC=copper(I) thiophene-2-carboxylate.
The efficiency of organocopper reagents in the displacement of allylic leaving groups has been well established during the past five decades. In sharp contrast, catalytic asymmetric version of this reaction using a chiral catalyst is a more recent field of research. This chapter presents an overview of tremendous studies towards the development of an “ideally” active catalyst achieving high regio- and enantioselectivities. The comparative reactivity and generality of peptides, phosphorus, as well as N-heterocyclic carbenes based catalysts are discussed in the first part. Then, relevant scope and synthetic applications are reviewed. Noteworthily, this chapter is restricted to C–C bond formation processes, excluding C–B and C–Si bond formations.
A. Quintard, J.-B. Langlois, D. Emery, J. Mareda, L. Guénée, A. Alexakis
"Conformationally Stabilized Catalysts by Fluorine Insertion: Tool for Enantioselectivity Improvement"
Chem. Eur. J.2011, 17, 13433-13437.
Frigid cats: The power of conformationally stabilized catalysts is demonstrated. By taking appropriate advantage of fluorine insertion (see scheme), purely conformational catalyst design led to a notable improvement in enantioselectivities from around 70 % to 91-98.5 % ee. The other advantage of this approach is the better understanding of the origin of the stereoselectivity in the given catalytic system.
D. Müller, M. Tissot, A. Alexakis
"New Experimental Conditions for Tandem hydroalumination/Cu-Catalyzed Asymmetric Conjugate Additions to β-Substituted Cyclic Enones"
Org. Lett.2011, 13, 3040-3043.
Readily available alkenylalanes, arising from hydroalumination of unprotected terminal alkynes, have been directly employed for the copper-catalyzed asymmetric conjugate addition (ACA) to β-substituted cyclic enones. The desired products, containing a quaternary stereogenic center, are generally obtained in good yields and enantioselectivities.
A. Quintard, A. Alexakis
"Highly enantioselective organocascade intermolecular iminium/enamine Michael addition on enals"
Chem. Commun.2011, 47, 7212-7214.
An unprecedented intermolecular iminium/enamine Michael addition on enals has been developed by taking advantage of the high reactivity of vinyl sulfones. This powerful organocascade allows for the rapid construction of attractive synthons in high enantioselectivities (typically 99% ee).
J. J. Murphy, A. Quintard, P. McArdle, A. Alexakis, J. C. Stephens
"Asymmetric Organocatalytic 1,6-Conjugate Addition of Aldehydes to Dienic Sulfones"
Angew. Chem. Int. Ed.2011, 50, 5095-5098.
An unprecedented 1,6-enamine conjugate addition exploiting the charge delocalization in 1,3-bis(sulfonyl) butadienes has been developed. By appropriately designing a Michael acceptor, unique reactivities were obtained for the formation of highly valuable dienes containing two versatile vinyl sulfones (see scheme, TMS=trimethylsilyl).
M. Tissot, A. Pérez Hernández, D. Müller, M. Mauduit, A. Alexakis
"Highly Enantioselective and Regioselective Copper-Catalyzed 1,4 Addition of Grignard Reagents to Cyclic Enynones"
Org. Lett.2011, 13, 1524-1527.
In this letter we describe an unusual result in terms of regioselectivity with respect to copper-catalyzed conjugate additions of various Grignard reagents to cyclic enynones. The use of Cu(OTf)2 and NHC ligand L1 as the catalyst combination in CH2Cl2 led to the unique formation of the 1,4 adduct. This selectivity does not follow the general trend previously observed in the literature using extended Michael acceptors. Moreover these reactions allowed for the creation of a quarternary stereogenic center with enantioselectivities up to 97% ee.
A. Quintard, A. Lefranc, A. Alexakis
"Highly Enantioselective Direct Vinylogous Michael Addition of γ-Butenolide to Enals"
Org. Lett.2011, 13, 1540-1543.
An unprecedented and simple direct vinylogous addition of deconjugated butenolide to enals has been developed in excellent stereoselectivities (>95% ee), with Aminal-PYrrolidine (APY) catalyst. This methodology allows for the efficient preparation of complex γ-butenolide from readily available renewable resources. Furthermore, preliminary mechanistic investigations have allowed for the better understanding of the origin of both stereoselectivities and of the observed high reactivities.
A. Quintard, A. Alexakis, C. Mazet
"Access to High Levels of Molecular Complexity by One-Pot Iridium/Enamine Asymmetric Catalysis"
Angew. Chem. Int. Ed.2011, 50, 2354-2358.
Independent workers with team spirit: A catalytic sequence that exploits the compatibility of (chiral) cationic iridium catalysts for the isomerization of primary allylic alcohols to aldehydes with organocatalysts has been developed for the highly enantioselective α functionalization of aldehydes (see scheme: up to 66 % yield, d.r. 49:1, 99 % ee). The reaction displayed useful generality with respect to both the nucleophile and the electrophile.
J.-B. Langlois, A. Alexakis
"Identification of a Valuable Kinetic Process in Copper-Catalyzed Asymmetric Allylic Alkylation"
Angew. Chem. Int. Ed.2011, 50, 1877-1881.
Copper bottomed: The application of a previously described process of dynamic kinetic asymmetric transformation to acyclic substrates allowed the identification of a relevant kinetic process in the title reaction (see scheme; CuTC= copper(I) thiophencarboxylate, Naphth= naphthyl). The optimization of the reaction conditions and generality of the method, as well as mechanistic considerations are disclosed.
The 1,2-sulfone rearrangement resulting from nucleophilic addition to bis activated vinyl-sulfones has been studied in more detail. Various nucleophiles activated by different types of catalysts (enamine, Brönsted base, thiourea) are able to promote such rearrangement in excellent yields and moderate to excellent enantioselectivities (up to 94% ee). Mechanistic studies have led to a better understanding of the mechanism and allowed its application to other electrophiles such as vinyl-sulfone acrylates.
C. Hawner, D. Müller, L. Gremaud, A. Felouat, S. Woodward, A. Alexakis
"Rhodium-Catalyzed Asymmetric 1,4-Addition of Aryl Alanes to Trisubstituted Enones: Binap as an Effective Ligand in the Formation of Quaternary Stereocenters"
Angew. Chem. Int. Ed.2010, 49, 7769-7772.
All for one and 1,4-all: Readily available aryl alanes are used in the rhodium-catalyzed asymmetric conjugate addition reaction with a variety of cyclic and acyclic enones. The enhanced reactivity of the system allows the use of the common binap ligand for the generation of quaternary benzylic stereocenters in excellent enantioselectivity (see scheme).
We present here the first catalytic desymmetrization of the 2,2′,6,6-tetrabromobiphenyl 1 and analogues, by a bromine-lithium exchange catalyzed by either diamines or diether derivatives (0.5 equiv.), yielding axially chiral compounds in high yield (up to 89%) and high enantioselectivity (up to 82%).
J. Mazuela, O. Pàmies, M. Diéguez, L. Palais, S. Rosset, A. Alexakis
"Fine-tunable monodentate phosphoroamidite and aminophosphine ligands for Rh-catalyzed asymmetric hydroformylation"
Tetrahedron: Asymmetry2010, 21, 2153-2157.
A biaryl-based monophosphoroamidite L1-L4a-f and aminophosphine L5-L7a-f ligand library was screened in the Rh-catalyzed asymmetric hydroformylation of several vinylarenes and heterocyclic olefins. Our results indicate that the selectivity is strongly dependent on the ligand parameters and on the substrate type. Enantioselectivities (up to 46%) were moderate in the hydroformylation of several vinylarenes S1-S5 and promising (up to 58%) for the more challenging heterocyclic olefins S6-S9.
C. Hawner, A. Alexakis
"Metal-catalyzed asymmetric conjugate addition reaction: formation of quaternary stereocenters"
Chem. Commun.2010, 46, 7295-7306.
All-carbon quaternary stereocenters are ubiquitous motifs in biological products and pharmaceutical agents. However, due to sterical reasons, these centers are not always easily accessible. The metalcatalyzed conjugate addition reaction to trisubstituted conjugated substrates presents a viable methodology to create quaternary centers. In this article, different ways of activating the conjugate system towards nucleophilic addition will be described. An overview will be given on the different types of quaternary centers that are accessible through the conjugate addition reaction.
J. Wencel-Delord, A. Alexakis, C. Crévisy, M. Mauduit
"Enantioselective 1,6-Conjugate Additionto Cyclic Dienones Catalyzed by theCu-DiPPAM Complex"
Org. Lett.2010, 12, 4335-4337.
In the presence of a Cu/DiPPAM catalytic system, various diorganozinc reagents realize 1,6-asymmetric conjugate addition on various cyclic five- and six-membered cyclic dienones, with complete regioselectivity and high ee’s (93-99%).
A. Quintard, A. Alexakis
"Highly Enantioselective One-Pot Copper-Catalyzed 1,4 Addition/Organocatalyzed α-Substitution of Enals"
Adv. Synth. Catal.2010, 352, 1856-1860.
The asymmetric copper-catalyzed addition of dialkylzinc to enals followed by organocatalyzed one-pot aldehyde α-functionalization has been accomplished providing CC, CCl or CF bond formation. These simple procedures led to the creation of two contiguous stereocenters in excellent enantioselectivities (typical ee=99%). This methodology has been applied in the synthesis of (2S,3S) isomer of Valnoctamide®.
S. Kehrli, D. Martin, D. Rix, M. Mauduit, A. Alexakis
"Formation of Quaternary Chiral Centers by N-Heterocyclic Carbene–Cu-Catalyzed Asymmetric Conjugate Addition Reactions with Grignard Reagents on Trisubstituted Cyclic Enones"
Chem. Eur. J.2010, 16, 9890-9904.
The copper-catalyzed conjugate addition of Grignard reagents to 3-substituted cyclic enones allows the formation of all-carbon chiral quaternary centers. We demonstrate in this article that N-heterocyclic carbenes act as efficient chiral ligands for this transformation. High enantioselectivities (up to 96 % ee) could be obtained for a variety of substrates.
C. Bournaud, E. Marchal, A. Quintard, S. Sulzer-Mossé, A. Alexakis
"Organocatalyst-mediated enantioselective intramolecular Michael addition of aldehydes to vinyl sulfones"
Tetrahedron: Asymmetry2010, 21, 1666-1673.
Chiral amines with a hydrogen bond donor promote the intramolecular conjugate addition of aldehydes to vinyl sulfones. Chiral cyclic sulfone-aldehydes are obtained in good yields with an ee of up to 82%.
D. Müller, C. Hawner, M. Tissot, L. Palais, A. Alexakis
"Creation of Quaternary Stereogenic Centers via Copper-Catalyzed Asymmetric Conjugate Addition of Alkenyl Alanes to α,β-Unsaturated Cyclic Ketones"
Synlett2010, 1694-1698.
SimplePhos ligands proved to be very powerful ligands in the generation of quaternary stereogenic centers by Michael addition of alkenyl-aluminum reagents to cyclic enones. Using commercially available and easily accessible alkenylbromides as alane precursors the present procedure offers a facile access to β-alkenyl-substituted cyclohexanones with high enantioselectivities up to 96%.
M. Tissot, D. Müller, S. Belot, A. Alexakis
"Enantioselective and Regiodivergent Copper-Catalyzed Conjugate Addition of Trialkylaluminium Reagents to Extended Nitro-Michael Acceptors"
Org. Lett.2010, 12, 2770-2773.
The first highly enantioselective and regiodivergent conjugate addition of trialkylaluminium reagents to nitrodienes and nitroenynes is described. By a design of the substrate and a fine-tuning of the reaction conditions, it is possible to selectively form the 1,4- or 1,6-adduct. The same combination of catalyst, copper source, and a ferrocene-based phosphine ligand afforded enantioselectivities up to 95% and 91%, respectively.
A. Quintard, A. Alexakis
"Asymmetric addition of α-hetero-disubstituted aldehydes to vinyl sulfones; formation of highly functionalized tetrasubstituted carbon centres"
Chem. Commun.2010, 46, 4085-4087.
Aminal–pyrrolidine catalysed addition of α-hetero-disubstituted aldehydes to vinyl sulfones is described in high enantioselectivity (ee up to 97%). The obtained adducts can easily be converted to enantioenriched synthons as for example 2,2-dialkylepoxide. Evidence for a kinetic resolution is also observed.
L. Palais, L. Babel, A. Quintard, S. Belot, A. Alexakis
"Copper-Catalyzed Enantioselective 1,4-Addition to α,β-Unsaturated Aldehydes"
Org. Lett.2010, 12, 1988-1991.
The first asymmetric Cu-catalyzed conjugate addition of dialkylzinc zinc reagents to a large scope of enals in presence of phosphoramidite, SimplePhos, or (R)-BINAP ligands with enantiomeric excesses up to 90% is reported. Moreover, ACA of Grignard reagents afforded moderate to good 1,4-regioselectivities with enantioselectivities up to 90%.
Open wide and say AAA: The copper-free asymmetric allylic alkylation reaction of Grignard reagents, catalyzed by N-heterocyclic carbenes, is reported for allyl bromide derivatives. This reaction offers good enantioselectivity and good to excellent γ regioselectivity, particularly for the formation of quaternary chiral centers (see scheme; Mes=mesityl).
F. Giacomina, D. Riat, A. Alexakis
"ω-Ethylenic Allylic Substrates as Alternatives to Cyclic Substrates in Copper- and Iridium-Catalyzed Asymmetric Allylic Alkylation"
Org. Lett.2010, 12, 1156-1159.
A new strategy to access highly enantioenriched cyclic compounds (up to 98%) is proposed using ω-ethylenic allylic substrates through a one-pot asymmetric allylic alkylation and ring-closing metathesis. Such starting compounds can be seen as synthetic equivalents of cyclic allylic substrates.
S. Belot, A. Quintard, N. Krause, A. Alexakis
"Organocatalyzed Conjugate Addition of Carbonyl Compounds to Nitrodienes/Nitroenynes and Synthetic Applications"
Adv. Synth. Catal.2010, 352, 667-695.
The purpose of this study is to point out the synthetic utility of a new class of Michael acceptors (nitrodienes and nitroenynes). The highly enantioselective organocatalytic Michael addition of carbonyl compounds to these functionalized nitroolefins has been carried out in the presence of (S)-diphenylprolinol silyl ether to achieve some interesting building blocks in high selectivities. The adducts thus obtained can be easily converted by taking advantage of the corresponding unsaturated carbon-carbon bond. In presence of the double bond, metathesis or electrophilic activation could be carried out whereas in the presence of the triple bond electrophilic activation could be conducted. We thus focused on a gold-catalyzed cyclization of the bis-homopropargylic alcohol to afford the corresponding substituted tetrahydrofuran. Then, we also demonstrated that organic and gold catalysts were compatible in a one-pot process. Indeed, we developed a one-pot enantioselective organocatalytic Michael addition to a nitroenyne followed by a gold-catalyzed acetalization/cyclization to achieve tetrahydrofuranyl ethers in high diastereo- and enantioselectivities with excellent yields.
J.-B. Langlois, A. Alexakis
"Copper-Catalyzed Asymmetric Allylic Alkylation of Racemic Cyclic Substrates: Application of Dynamic Kinetic Asymmetric Transformation (DYKAT)"
Adv. Synth. Catal.2010, 352, 447-457.
The copper-catalyzed asymmetric allylic alkylation (AAA) is of great interest in organic synthesis. This reaction was extensively studied using a broad range of substrates, ligands and organometallic reagents. However, the use of racemic substrates was still limited. Although some processes of kinetic resolution are reported in the literature, no examples of quantitative deracemization are described as is the case for the Pd-catalyzed allylic alkylation. We present here a full account of our investigations through the development of the first example of such a process in copper-catalyzed AAA. High enantioselectivities (up to 99% ee), scope of the reaction and mechanistic considerations are reported herein.
L. Palais, C. Bournaud, L. Micouin, A. Alexakis
"Copper-Catalysed Ring Opening of Polycyclic meso-Hydrazines with Trialkylaluminium Reagents and SimplePhos Ligands"
Chem. Eur. J.2010, 16, 2567-2573.
meso-Hydrazines could be desymmetrised by ring-opening reactions by using various metal catalysts to form substituted cyclopentenes, which have a high synthetic potential. Herein, we report the asymmetric copper-catalysed ring opening of a range of polycyclic hydrazines with trialkylaluminium reagents and SimplePhos ligands with both high isolated yields and enantioselectivities of up to 95 %.
A. Quintard, S. Belot, E. Marchal, A. Alexakis
"Aminal-Pyrrolidine Organocatalysts - Highly Efficient and Modular Catalysts for α-Functionalization of Carbonyl Compounds"
Eur. J. Org. Chem.2010, 927-936.
The substitution of the 4-position of hydroxyproline by aphenol group, together with an aminal on the 2-position, gave a synergistic effect leading to two powerful complementary organocatalysts. They show excellent enantiocontrol in the α-functionalization of a wide range of linear/branched aldehydes and ketones, including Michael additions to ethenediyl disulfones or nitrostyrene and α-amination. We obtained ees up to 98.5 % with low catalyst loadings (down to 1 mol-%). As a proof of efficiency, TOFs of up to 1000 h-1 could be obtained.
M. Welker, S. Woodward, A. Alexakis
"Tandem Reactions with Chiral Enolates: Preparation of Allylic Alcohols via Trapping with Vinyl Oxiranes"
Org. Lett.2010, 12, 576-579.
An opening of vinyl oxiranes has been accomplished with Zn and Al enolates resulting from asymmetric conjugate addition reactions on cyclic enones. This novel tandem procedure affords the adducts in moderate to good yields, enantioselectivities up to 98%, and moderate to good cis/trans selectivities. This provides potentially useful synthetic substrates to prepare complex bicyclic compounds.
C. Ladjel, N. Fuchs, L. Gremaud, A. Alexakis
"Copper catalysed kinetic resolution of cyclic alkenyl cyclopropane malonate with organoaluminiun and grignard reaggents"
Synlett2010, 317-320.
We report herein the first copper-catalysed kinetic resolution of alkenyl cyclopropane malonates with organoaluminium and Grignard reagents. The conjugate products were exclusively obtained on five- and six-membered-ring substrates. After optimization of the reaction conditions, we observed good conversions and enantiomeric excesses using ferrocene-based ligands on five-membered-ring substrates, and phosphoramidite ligands on six-membered rings.
S. Belot, K. A. Vogt, C. Besnard, N. Krause, A. Alexakis
"Enantioselective One-Pot Organocatalytic Michael Addition/Gold-Catalyzed Tandem Acetalization/Cyclization"
Angew. Chem. Int. Ed.2009, 48, 8923-8926.
Au-rganocatalytic reaction: A one-pot process consisting of a Michael addition to a nitroenyne and a subsequent acetalization/cyclization is reported (see scheme; TMS=trimethylsilyl), which results in the formation of nitro-substituted tetrahydrofuranyl ethers with high diastereo- and enantioselectivities. Organocatalysis and gold catalysis are compatible and complementary in a one-pot process.
E. Raluy, O. Pàmies, M. Diéguez, S. Rosset, A. Alexakis
"Sugar-based phosphite and phosphoroamidite ligands for the Cu-catalyzedasymmetric 1,4-addition to enones"
Tetrahedron: Asymmetry2009, 20, 2167-2172.
J. Wencel, M. Mauduit, H. Hénon, S. Kehrli, A. Alexakis
"Chiral, Chelating, Hydroxyalkyl and Hydroxyaryl N-Heterocyclic Carbenes: Design, Synthesis, andApplication in Copper-Catalyzed Asymmetric Conjugate Addition (Cu-ACA)"
Aldrichim. Acta2009, 42, 43-50.
Since their discovery in 1968 by Öfele and Wanzlick, and their first isolation in the free state by Arduengo in the early 1990s, N-heterocyclic carbene (NHC) ligands have received a growing attention from the scientific community, notably in organometallic chemistry. These ligands are likely to surpass in popularity well-known phosphorus-based ligands because of their remarkable ability to establish strong bonds with the metal center and their capacity to permit significant doping of catalyst activity in a wide range of chemical transformations such as olefin metathesis, carbon-carbon and carbon-nitrogen cross-coupling reactions, hydrogenation, and hydrosilylation.
A. Quintard, A. Alexakis
"Organocatalytic Addition on 1,2-Bis(sulfone)vinylenes Leading to an Unprecedented Rearrangement"
Chem. Eur. J.2009, 15, 11109-11113.
An unprecedented rearrangement of 1,2-bis(sulfone)vinylenes used in aminocatalysis led to the formation of highly useful gem-disulfones (see scheme). By using aminal-pyrrolidine organocatalysts, the 1,2-sulfone shift was generalised, leading to highly versatile adducts using both ketones and aldehydes. It represents a valuable alternative for the -alkylation of carbonyl compounds.
SimplePhos ligands represent a novel class of monodentate chiral ligands based on a chiral amine moiety and flexible diaryl groups on the phosphorous atom. They can be easily prepared by two different pathways and they can be highly functionalised. Herein we report the copper-catalysed asymmetric conjugate addition of diethyl zinc and trialkylaluminium reagents with SimplePhos ligands, which gives high enantioselectivity with cyclic enones, acyclic enones and nitro-olefins, with up to 98.6 % ee. Of particular interest is the reaction of trialkylaluminium reagents with a wide range of 3-substituted enones, thus allowing the formation of stereogenic quaternary carbon centres.
C. Ladjel, N. Fuchs, J. Zhao, G. Bernardinelli, A. Alexakis
"New bifunctional substrates for Copper-catalysed asymmetric conjugate addition reactions with trialkylaluminium"
Eur. J. Org. Chem.2009, 4949-4955.
E. Raluy, O. Pàmies, M. Diéguez, S. Rosset, A. Alexakis
"Furanoside phosphite-phosphoroamidite and diphosphoroamidite ligands for Cu-catalyzed asymmetric 1,4-addition reactions"
Tetrahedron: Asymmetry2009, 20, 1930-1935.
K. N. Gavrilov, E. B. Benetskiy, T. B. Grishina, E. A. Rastorguev, M. G. Maksimova, S. V. Zheglov, V. A. Davankov, B. Schäffner, A. Börner, S. Rosset, G. Bailat, A. Alexakis
"Bulky P*-Chirogenic Diazaphospholidines as monodentate ligands for asymmetric catalysis"
Eur. J. Org. Chem.2009, 3923-3929.
R. Millet, L. Gremaud, T. Bernardez, L. Palais, A. Alexakis
"Copper catalysed asymmetric ring opening reaction of oxabenzonorbornadienes with grignard and aluminium reaggents"
Synthesis2009, 2101-2112.
A highly enantioselective method for the copper-catalyzed desymmetrization of oxabenzonorbornadienes with aluminum reagents and SimplePhos as chiral ligand has been developed. The same reaction with Grignard reagents is also reported. A wide range of alkyl chains have been used with moderate to high enantioselectivity and high trans selectivity. The transfer of a methyl group is also reported with high enantiomeric and diastereomeric excess and yields for different substrates. We finally have been able to perform the first trans enantioselective desymmetrization of oxabenzonorbornadienes with an aromatic group.
Different classes of prochiral polyhalide compounds have been tested in a chiral bromine-lithium exchange in the presence of different diamines with enantiomeric excesses of up to 63%.
R. Millet, T. Bernardez, L. Palais, A. Alexakis
"Copper-catalyzed desymmetrization of oxabenzonorbornadienes with aluminum reagents"
Tetrahedron Lett.2009, 50, 3474-3477.
The desymmetrization of oxabenzonorbornadienes with aluminum reagents and SimplePhos as chiral ligand is described. The corresponding homoallylic alcohols are obtained in high yield, diastereoselectivity, and enantiomeric excess. Furthermore the first anti enantioselective desymmetrization with aromatic nucleophiles is reported.
S. Sulzer-Mossé, A. Alexakis, J. Mareda, G. Bollot, G. Bernardinelli, Y. Filinchuk
"Enantioselective organocatalytic conjugate addition of aldehydes to vinyl sulfones and vinyl phosphonates as challenging Michael accepptors"
Chem. Eur. J.2009, 15, 3204-3220.
Chiral amines with a pyrrolidine framework catalyze the enantioselective conjugate addition of a broad range of aldehydes to various vinyl sulfones and vinyl phosphonates in high yields and with enantioselectivities up to >99% ee. This novel process provides synthetically useful chiral γ-gem-sulfonyl or phosphonyl aldehydes which can be widely functionalized with retention of the enantiomeric excess. Mechanistic insights including DFT calculations are explored in detail.
D. Polet, X. Rathgeb, C. A. Falciola, J.-B. Langlois, S. El Hajjaji, A. Alexakis
"Enantioselective Iridium-catalysed allylic arylation"
Chem. Eur. J.2009, 15, 1205-1216.
We describe herein the development of the first iridium-catalyzed allylic substitution using arylzinc nucleophiles. High enantioselectivities were obtained from the reactions, which used commercially available Grignard reagents as the starting materials. This methodology was also shown to be compatible with halogen/metal exchange reactions. Its synthetic potential is demonstrated by its application towards the formal synthesis of (+)-sertraline.
E. B. Benetskii, V. A. Davankov, P. V. Petrovskii, E. A. Rastorguev, T. B. Grishina, K. N. Gavrilov, S. Rosset, G. Bailat, A. Alexakis
"New P-Chiral polyfluoroalkyl phosphoramidite ligand in asymmetric transformations catalysed by palladium and copper complexes"
Russ. J. Org. Chem.2008, 44, 1846-1848.
C. A. Falciola, A. Alexakis
"High diversity on simple substrates: 1,4 dihalo-2-butenes and other difunctionalised allylic halides for copper-catalysed SN2' reactions"
Chem. Eur. J.2008, 14, 10615-10627.
C. Hawner, K. Li, V. Cirriez, A. Alexakis
"Copper-catalysed asymmetric conjugate addition of aryl aluminium reaggents to trisubstituted enones: construction of aryl-substituted quaternary centers"
Angew. Chem. Int. Ed.2008, 47, 8211-8214.
S. Belot, A. Massaro, A. Tenti, A. Mordini, A. Alexakis
"Enantioselective organocatalytic conjugate addition of aldehydes to nitrodienes"
Org. Lett.2008, 10, 4557-4560.
S. Belot, S. Sulzer-Mossé, S. Kehrli, A. Alexakis
"Enantioselective organocatalytic conjugate addition of α-aminoketone to nitroolefins"
Chem. Commun.2008, 4694-4696.
The enantioselective organocatalytic conjugate addition of α-aminoketone to nitroolefins is reported.
A. Quintard, C. Bournaud, A. Alexakis
"Diversity-Oriented Synthesis towards Conceptually New Highly Modular Aminal-Pyrrolidine Organocatalysts"
Chem. Eur. J.2008, 14, 7504-7507.
New family member: A conceptually new family of modular aminal-pyrrolidine organocatalysts was prepared by diversity-oriented synthesis. The catalytic properties of these organocatalysts could easily be tuned by varying the different substituents on the aminal part. Good yields and enantioselectivities up to 91 % were obtained in Michael additions to nitroolefins or vinyl sulfones.
A. Alexakis, J. E. Bäckvall, N. Krause, O. Pàmies, M. Diéguez
"Enantioselective copper-catalysed conjugate addition and allylic substitution reactions"
Chem. Rev.2008, 108, 2796-2823.
R. Millet, A. Alexakis
"Simplephos as efficient ligands for the copper-catalysed kinetic resolution of cyclic vinyloxiranes with grognard reaggents"
Synlett2008, 12, 1797-1800.
A. Alexakis, M. Vuagnoux-d'Augustin, D. Martin, S. Kehrli, L. Palais, H. Hénon, C. Hawner
"Formation of all-carbon quaternary centers by copper-catalysed asymmetric conjugate addition"
CHIMIA2008, 62, 461-464.
C. A. Falciola, K. Tissot-Croset, H. Reyneri, A. Alexakis
"β- and γ-disubstituted olefins: susbtrates for copper-catalysed asymmetric allylic substitution"
Adv. Synth. Catal.2008, 350, 1090-1100.
A. Alexakis, M. Vuagnoux-d'Augustin, D. Martin, S. Kehrli
"Formation of all-carbon chiral quaternary centers by copper catalysed asymmetric cojugate addition"
Latvija kimijas zurnals2007, 373-377.
M. Vuagnoux-d'Augustin, A. Alexakis
"Influence of the double-bond geometry of the Michael acceptor on copper-catalysed asymmetric conjugate addition"
Eur. J. Org. Chem.2007, 5852-5860.
Q. Perron, A. Alexakis
"Synthesis and application of a new pseudo C2-symmetric tertiary diamine for the enantioselective addition of MeLi to aromatic imines"
Tetrahedron: Asymmetry2007, 18, 2503-2506.
M. Vuagnoux-d'Augustin, A. Alexakis
"Copper catalysed asymmetric conjugate addition of trialkylaluminuim reaggents to trisubstituted enones: construction of chiral quaternary centers"
Chem. Eur. J.2007, 13, 9647-9662.
L. Palais, I. S. Mikhel, C. Bournaud, L. Micouin, C. A. Falciola, M. Vuagnoux-d'Augustin, S. Rosset, G. Bernardinelli, A. Alexakis
"SimplePhos monodentate ligands: Synthesis and application in copper-catalysed reactions"
Angew. Chem. Int. Ed.2007, 46, 7462-7465.
M. Vuagnoux-d'Augustin, A. Alexakis
"Tandem asymmetric conjugate addition-enolacetates formation of enantiomerically enriched zinc and aluminium enolates"
Tetrahedron Lett.2007, 48, 7408-7412.
S. Sulzer-Mossé, M. Tissot, A. Alexakis
"First enantioselective organocatalytic conjugate addition of aldehydes to vinyl phosphonates"
Org. Lett.2007, 9, 3749-3752.
A. Alexakis, S. El Hajjaji, D. Polet, X. Rathgeb
"Iridium-Catalysed asymmetric allylic substitution with aryl zinc reaggents"
Org. Lett.2007, 9, 3393-3395.
M. Vuagnoux-d'Augustin, S. Kehrli, A. Alexakis
"Enantioselective copper catalysed conjugate addition to 2- or 3- substituted cyclopent-2-ene-1-ones: Construction of stereogenic quaternary carbon centers"
Synlett2007, 2057-2060.
S. Sulzer-Mossé, A. Alexakis
"Chiral amines as organocatalysts for asymmetric conjugate addition to nitroolefins and vinyl sulfones via enamine activation"
Chem. Commun.2007, 3123-3135.
S. Sulzer-Mossé, M. Laars, K. Kriis, T. Kanger, A. Alexakis
"Synthesis and use of 3,3'-bimorpholine derivatives in asymmetric Michael addition and intramolecular aldol reaction"
Synthesis2007, 1729-1732.
C. A. Falciola, A. Alexakis
"1,4-Dichloro- and 1,4-Dibromo-2-butenes as Substrate for Cu-catalyzed Asymmetric Allylic Substitution"
Angew. Chem. Int. Ed.2007, 46, 2619-2622.
K. Li, A. Alexakis
"Asymmetric conjugate addition to α-halo enones : Dramatic effect of styrene on the enantioselectivity"
Angew. Chem. Int. Ed.2006, 45, 7600-7603.
A.-S. Chauvin, G. Bernardinelli, A. Alexakis
"Determination of the absolute configuration of chiral cyclic alcohols using diamine derivatizing agents by 31P NMR spectroscopy"
Tetrahedron: Asymmetry2006, 17, 2203-2209.
C. A. Falciola, K. Tissot-Croset, A. Alexakis
"β-Disubstituted Allylic Chloride: Substrate for th Cu-Catalyzed Asymmetric SN2' Reaction"
Angew. Chem. Int. Ed.2006, 45, 5995-5998.
C. Bournaud, C. Falciola, T. Lecourt, S. Rosset, A. Alexakis, L. Micouin
"On the use of phosphramidite ligands in copper-catalyzed asymmetric transformations with trialkylaluminium reagents"
Org. Lett.2006, 8, 3581-3584.
D. Martin, S. Kehrli, M. d'Augustin, H. Clavier, M. Mauduit, A. Alexakis
"Copper-catalyzed asymmetric conjugate addition of Grignard reagents to trisubstituted enones. Construction of all-carbon quaternary centers"
J. Am. Chem. Soc.2006, 128, 8416-8417.
A.-S. Chauvin, A. Alexakis
"Chiral trimethylsilylated C2-symmetrical diamines as phosphorous derivatizing agents for the determination of the enantiomeric excess of chiral alcohols by 1H NMR"
Beilstein J. Org. Chem2006, 2,.
S. Mossé, M. Laars, K. Kriis, T. Kanger, A. Alexakis
"3,3'-Bimorpholine derivatives as a new class of organocatalysts for asymmetric michael addition"
Org. Lett.2006, 8, 2559-2562.
S. Gille, N. Cabello, J.-C. Kizirian, A. Alexakis
"A new pseudo C2-symmetric tertiary diamine for the enantioselective addition of MeLi to aromatic imines"
Tetrahedron: Asymmetry2006, 17, 1045-1047.
S. Mossé, O. Andrey, A. Alexakis
"The use of N-iPr-2,2'-bipyrrolidine derivatives as organocatalysts for asymmetric Michael additions"
CHIMIA2006, 60, 216-219.
D. Polet, A. Alexakis, K. Tissot-Croset, C. Corminboeuf, K. Ditrich
"Phosphoramidite Ligands in Iridium-Catalyzed Allylic Substitution"
Chem. Eur. J.2006, 12, 3596-3609.
I. S. Mikhel, G. Bernardinelli, A. Alexakis
"Chiral P-monodentate phosphoramidite and phosphite ligands forthe enantioselective Pd-catalyzed allylic alkylation"
Inorg. Chim. Acta2006, 359, 1826-1836.
A. Alexakis, D. Polet, C. Bournaud, M. Bonin, L. Micouin
"Phophoramidite ligands for the enantioselective iridium-catalyzed asymmetric hydroboration of meso-bicyclic hydrazines"
Tetrahedron: Asymmetry2005, 16, 3672-3675.
C. L. Winn, F. Guillen, J. Pytkowicz, S. Roland, P. Mangeney, A. Alexakis
"Enantioselective copper catalysed 1,4-conjugate addition reactions using chiral N-heterocyclic carbenes"
J. Organomet. Chem.2005, 690, 5672-5695.
N. Cabello, J.-C. Kizirian, S. Gille, A. Alexakis, G. Bernardinelli, L. Pinchard, J.-C. Caille
"Simple 1,2-Diamine Ligands for Asymmetric Addition of Aryllithium Reagents to Imines"
Eur. J. Org. Chem.2005, 4835-4842.
N. Fuchs, M. d’Augustin, M. Humam, A. Alexakis, R. Taras, S. Gladiali
"Asymmetric conjugate addition of metal alkyl reagents catalyzed by copper complexes with BINPO, a hemilabile P,O-heterobidentate axially chiral ligand"
Tetrahedron: Asymmetry2005, 16, 3143-3146.
K. Li, A. Alexakis
"Copper catalyzed tandem asymmetric conjugate addition cyclization reaction in presence of chiral phosphoramidite ligands"
Tetrahedron Lett.2005, 46, 8019-8022.
J.-C. Kizirian, N. Cabello, L. Pinchard, J.-C. Caille, A. Alexakis
"Enantioselective addition of MeLi to aromatic imines catalyzed by C2-symmetric tertiary diamine"
Tetrahedron2005, 61, 8939-8946.
K. Li, A. Alexakis
"Copper catalyzed asymmetric conjugate addition-bromination of α, β unsaturated ketones : a highly effective one pot reaction for the synthesis of chiral α bromo β alkyl ketone"
Tetrahedron Lett.2005, 46, 5823-5826.
A. Alexakis, V. Albrow, K. Biswas, M. d'Augustin, O. Prieto, S. Woodward
"Highly enantioselective copper(I)-phosphoramidite-catalysed additions of organoaluminium reagents to enones"
Chem. Commun.2005, 2843-2845.
E. Vrancken, A. Alexakis, P. Mangeney
"Organolithium chiral Lewis base BF3 : versatile combination for the enantioselective desymmetrisation of meso-epoxides"
Eur. J. Org. Chem.2005, 1354-1366.
A. Alexakis, A. Tomassini, O. Andrey, G. Bernardinelli
"Diastereoselective alkylation of (Arene)tricarbonyl-chromium and ferrocene complexes using a chiral C2-symmetrical 1,2 diamine as auxiliary"
Eur. J. Org. Chem.2005, 1332-1339.
M. d'Augustin, L. Palais, A. Alexakis
"Enantioselective copper-catalyzed conjugate addition to trisubstituted cyclohexenones: construction of stereogenic quaternary centers"
Angew. Chem. Int. Ed.2005, 44, 1376-1378.
D. Polet, A. Alexakis
"Cu-catalyzed asymmetric 1,4-addition of Me3Al to nitroalkenes. Synthesis of (+)-Ibuprofen"
Tetrahedron Lett.2005, 46, 1529-1532.
K. Tissot-Croset, D. Polet, S. Gille, C. Hawner, A. Alexakis
"Synthesis and use of a phosphoramidite ligand for the copper-catalyzed enantioselective allylic substitution. Tandem allylic substitution-ring closing metathesis"
Synthesis2004, 2586-2590.
O. Andrey, A. Alexakis, A. Tomassini, G. Bernardinelli
"The use of N-alkyl-2,2'-bipyrrolidine derivatives as organocatalysts for the asymmetric Michael addition of ketones and aldehydes to nitroolefins"
Adv. Synth. Catal.2004, 346, 1147-1168.
A. Alexakis, D. Polet, S. Rosset, S. March
"Biphenol-based phosphoramidite ligands for the enantioselective copper-catalyzed conjugate addition of diethylzinc"
J. Org. Chem2004, 69, 5660-5667.
F. Amiot, L. Cointeaux, E. J. Silve, A. Alexakis
"Enantioselective nucleophilic addition of organometallic reagents to quinoline: regio-, stereo- and enantioselectivity"
Tetrahedron2004, 60, 8221-8231.
A.-S. Chauvin, G. Bernardinelli, A. Alexakis
"Determination of the Absolute Configuration of Chiral Aryl-alkyl Carbinols using Organophosphorous Diamine Derivatizing Agents by 31P NMR Spectroscopy"
Tetrahedron: Asymmetry2004, 15, 1857-1879.
A. M. Arink, T. W. Braam, R. Keeris, J. T. . B. . H. Jastrzebski, C. Benhaim, S. Rosset, A. Alexakis, G. van Koten
"Copper(I) thiolate catalysts in asymmetric conjugate addition reactions"
Organic Lett.2004, 6, 1959-1962.
N. Cabello, J.-C. Kizirian, A. Alexakis
"Enantioselective addition of aryllithium reagents to aromatic imines mediated by 1,2-diamine ligands"
Tetrahedron Lett.2004, 45, 4639-4642.
O. Equey, A. Alexakis
"Enantioselective opening of cyclic vinyl epoxides with organoaluminium reagents catalysed by copper salts"
Tetrahedron: Asymmetry2004, 15, 1531-1536.
O. Equey, E. Vrancken, A. Alexakis
"Regioselective SN2 opening of vinylic epoxides with trialkylzincates and tetralkylaluminates"
Eur. J. Org. Chem.2004, 2151-2159.
O. Equey, A. Alexakis
"Enantioselective catalytic rearrangement of cyclohexene oxide with new homochiral bis-lithium amide bases"
Tetrahedron: Asymmetry2004, 15, 1069-1072.
A. Alexakis, S. Gille, F. Prian, S. Rosset, K. Ditrich
"Practical, solvent-free, one-pot synthesis of C2-symmetrical secondary amines"
Tetrahedron Lett.2004, 45, 1449-1451.
O. Andrey, A. Vidonne, A. Alexakis
"Organocatalytic Michael addition, a convenient tool in total synthesis. First asymmetric synthesis of (-)-botryodiplodin"
Tetrahedron Lett.2003, 44, 7901-7904.
O. Andrey, A. Alexakis, G. Bernardinelli
"Asymmetric Michael addition of α-hydroxy aldehydes to nitroolefins catalyzed by chiral diamine"
Org. Lett.2003, 5, 2559-2561.
A. Alexakis, C. L. Winn, F. Guillen, J. Pytkowicz, S. Roland, P. Mangeney
"Asymmetric synthesis with N-heterocyclic carbenes. Application to the copper catalyzed conjugate addition"
Adv. Synth. Catal.2003, 345, 345-348.
A. Alexakis, S. March
"Tandem enantioselective conjugate addition-cyclopropanation. Application to natural product synthesis"
J. Org. Chem2002, 67, 8753-8757.
L. Mediavilla Urbaneja, A. Alexakis, N. Krause
"Epimerization and kinetic resolution in copper-catalyzed enantioselective 1,4-additions of organozinc reagents to 6-substituted cyclohex-2-enones"
Tetrahedron Lett.2002, 43, 7887-7890.
A. Alexakis, C. Benhaim, S. Rosset, M. Humam
"Dramatic enhancement of the enantiomeric excess in asymmetric conjugate addition reaction using new experimental conditions"
J. Am. Chem. Soc.2002, 124, 5262-5263.
F. Guillen, C. L. Winn, A. Alexakis
"Enantioselective copper-catalyzed conjugate addition using chiral diaminocarbene ligands"
Tetrahedron: Asymmetry2001, 12, 2083-2086.
A. Alexakis, S. Rosset, J. Allamand, S. March, F. Guillen, C. Benhaim
"Novel biphenol phosphoramidite ligands for the enantioselective copper-catalyzed conjugate addition of dialkyl zincs"
Synlett2001, 1375-1378.
F. Mazé, M. Purpura, F. Bernaud, P. Mangeney, A. Alexakis
"Regio- and diastereoselective SN2' or SN2'' reactions on chiral acetals of cyclic aldehydes promoted by PhCu, BF3"
Tetrahedron: Asymmetry2001, 12, 1957-1960.
A. Alexakis, A.-S. Chauvin
"Determination of the enantiomeric excess of chiral carboxylic acids by 31P NMR with C2 symmetrical diamines"
Tetrahedron: Asymmetry2001, 12, 1411-1415.
A. Alexakis, A.-S. Chauvin, R. Stouvenel, E. Vrancken, S. Mutti, P. Mangeney
"A practical and efficient synthesis of chiral N,N-disubstituted C2 symmetric diamines derived from (R,R)-1,2-diaminocyclohexane"
Tetrahedron: Asymmetry2001, 12, 1171-1178.
A. Alexakis, I. Aujard, J. Pytkowicz, S. Roland, P. Mangeney
"Unusually facile palladium catalysed oxidation of imidazolidines and oxazolidines"
J. Chem. Soc., Perkin Trans. 12001, 949-951.
A. Alexakis, G. P. Trevitt, G. Bernardinelli
"Tandem enantioselective conjugate addition-electrophile trapping reactions. Application in the formation of syn or anti aldols"
J. Am. Chem. Soc.2001, 123, 4358-4359.
A. Alexakis, C. Malan, L. Lea, C. Benhaim, X. Fournioux
"Enantioselective copper-catalyzed SN2' substitution with Grignard reagents"
Synlett2001, 927-930.
A. Alexakis, J. Burton, J. Vastra, C. Benhaim, X. Fournioux, A. van den Heuvel, J.-M. Levêque, F. Mazé, S. Rosset
"Synthesis and application of chiral phosphorus ligands derived from TADDOL for the asymmetric conjugate addition of diethylzinc to enones"
Eur. J. Org. Chem.2000, 4011-4027.
A. Alexakis, A.-S. Chauvin
"TADDOL organophosphorus derivatising agents for the determination of the enantiomeric excess of alcohols and carboxylic acids by 31P and 1H NMR spectroscopy"
Tetrahedron: Asymmetry2000, 11, 4245-4248.
A. Alexakis, A. Tomassini, C. Chouillet, S. Roland, P. Mangeney, G. Bernardinelli
"A new efficient synthesis of (R,R)-2,2'-bipyrrolidine: an interesting chiral 1,2-diamine with C2 symmetry."
Angew. Chem. Int. Ed.2000, 39, 4093-4095.
A. Alexakis, E. Vrancken, P. Mangeney
"Effect of BF3·Et2O reagent on the base-promoted rearrangements of epoxides attached to eight-membered rings"
J. Chem. Soc., Perkin Trans. 12000, 3354-3355.
A. Alexakis, C. Benhaïm, X. Fournioux, A. van den Heuvel, J.-M. Levêque, S. March, S. Rosset
"Catalytic asymmetric conjugate addition on macrocyclic and acyclic enones. Synthesis of R-(-)-Muscone"
Synlett1999, 1811-1813.
F. Rose-Munch, V. Gagliardini, A. Perrotey, J.-P. Tranchier, E. Rose, P. Mangeney, A. Alexakis, T. Kanger, J. Vaissermann
"Two-step synthesis of homochiral monoaminals of tricarbonylphthalaldehydechromium complex"
Chem. Commun.1999, 2061-2062.
A. Alexakis, J. Vastra, J. Burton, C. Benhaim, P. Mangeney
"Asymmetric conjugate addition of diethylzinc to enones with chiral phosphorus ligands derived from TADDOL"
Tetrahedron Lett.1998, 39, 7869-7872.
D. Brasseur, H. Rezaei, A. Fuxa, A. Alexakis, P. Mangeney, I. Marek, J. F. Normant
"First diastereoselective asymmetric carbometallation of chiral vinyl metals"
Tetrahedron Lett.1998, 39, 4821-4824.
P. Mangeney, L. Hamon, S. Raussou, N. Urbain, A. Alexakis
"Radical cyclizations of 1,4-dihydropyridines. Synthesis of chiral fused nitrogen heterocycles. Synthesis of Lupinine and Epilupinine"
Tetrahedron1998, 54, 10349-10362.
A. Alexakis, J. Burton, J. Vastra, P. Mangeney
"Asymmetric conjugate addition of diethyl zinc to enones with chiral phosphine ligands"
Tetrahedron: Asymmetry1997, 8, 3987-3990.
A. Alexakis, J. Varta, J. Burton, P. Mangeney
"Asymmetric conjugate addition of diethyl zinc to enones with tartrate chiral phosphite ligands"
Tetrahedron: Asymmetry1997, 8, 3193-3196.
A. Alexakis, J. Vasta, P. Mangeney
"Acceleration of the conjugate addition of diethyl zinc to enones by either Cu(OTf)2 or trivalent phosphorus ligands"
Tetrahedron Lett.1997, 38, 7745-7748.
F. M. Bohnen, R. Goddard, A. B. . E. Minidis, A. Alexakis, A. Pfaltz
"A copper (II) complex of a new chiral tridentate imidazoline ligand"
Acta Crystallographica1997, C53, 1236-1238.
J. P. Tierney, A. Alexakis, P. Mangeney
"Catalytic enantioselective deprotonation of meso-epoxides utilising homochiral bis-lithium amide bases"
Tetrahedron: Asymmetry1997, 8, 1019-1022.
A. Alexakis, P. Mangeney
"Chiral aminals in asymmetric synthesis"
In Advanced Asymmetric Synthesis; G. . R. Stephenson (Ed.); Chapman & Hall: London, 1996; Ch. 5; p. 93.
A. Alexakis, F. Mhamdi, F. Lagasse, P. Mangeney
"Asymmetric cleavage of chiral α,β-ethylenic acetals by organolithium reagents"
Tetrahedron: Asymmetry1996, 7, 3343-3346.
A. Alexakis, P. Mangeney, N. Lensen, J.-P. Tranchier, R. Gosmini, S. Raussou
"Chiral Aminals: Powerful auxiliaries in asymmetric synthesis"
Pure Appl. Chem.1996, 68, 531-534.
H. Rakotoarisoa, R. Guttierez Perez, P. Mangeney, A. Alexakis
"Remote asymmetric induction. New mechanistic insights concerning the SN' and SN" substitution in organocopper chemistry"
Organometallics1996, 15, 1957-1959.
S. Raussou, N. Urbain, P. Mangeney, A. Alexakis, N. Platzer
"Preparation of chiral hexahydroquinolizinones and tetrahydroindolizinones by regio- and diastereoselective sonochemical cyclization of chiral dihydropyridines"
Tetrahedron Lett.1996, 37, 1599-1602.
A. Alexakis, T. Kanger, P. Mangeney, F. Rose-Munch, A. Perrotey, E. Rose
"Enantioselective ortho-lithiation of benzaldehyde chromiumtricarbonyl complex"
Tetrahedron: Asymmetry1995, 6, 2135-2138.
A. Alexakis, N. Lensen, J.-P. Tranchier, P. Mangeney, J. Feneau-Dupont, J.-P. Declercq
"Chiral aminal templates: Diastereoselective addition to hydrazones; an asymmetric synthesis of α-amino aldehydes"
Synthesis1995, 1038-1050.
A. Alexakis, T. Kanger, P. Mangeney, F. Rose-Munch, A. Perrotey, E. Rose
"Enantioselective ortho-lithiation of aminals of benzaldehyde chromiumtricarbonyl complex"
Tetrahedron: Asymmetry1995, 6, 47-50.
A. Alexakis, J. C. Frutos, P. Mangeney, A. . I. Meyers, H. Moorlag
"Determination of enantiomeric purity of hydroxy biaryls using 1H and 31P NMR on their diazaphospholidine derivatives"
Tetrahedron Lett.1994, 35, 5125-5128.
S. Raussou, R. Gosmini, P. Mangeney, A. Alexakis, M. Commerçon
"Regio and enantioselective synthesis of 4-carbomethoxymethy-1,4-dihydropyridines"
Tetrahedron Lett.1994, 35, 5433-5436.
A. Alexakis, J. C. Frutos, S. Mutti, P. Mangeney
"Chiral diamines for a new protocol to determine the enantiomeric composition of alcohols, thiols and amines by 31P, 1H, 13C and 19F NMR"
J. Org. Chem.1994, 59, 3326-3334.
P. Mangeney, R. Gosmini, S. Raussou, M. Commercon, A. Alexakis
"Preparation and utilization of chiral dihydropyridines. Synthesis of chiral indoloquinolizines and benziquinolizines"
J. Org. Chem.1994, 59, 1877-1888.
A. Alexakis, J. C. Frutos, P. Mangeney
"An easy and fast way to determine the enantiomeric purity of substituted cyclanones"
Tetrahedron: Asymmetry1993, 4, 2431-2434.
A. Alexakis, J. Frutos, P. Mangeney
"Chiral phosphorus ligands for the asymmetric conjugate addition of organocopper reagents"
Tetrahedron: Asymmetry1993, 4, 2427-2430.
A. Alexakis, R. Sedrani, N. Lensen, P. Mangeney
"Chiral aminal templates. Diastereo- and enantioselectivity in 1,4 (conjugate) and 1,2 additions with organometallic reagents"
In Organic Synthesis via Organometallics; D. Enders, H.-J. Gais, W. Keim (Eds.); Vieweg: Wiesbaden, 1993; p. 1.
A. Alexakis, P. Mangeney, I. Marek, F. Rose-Munch, E. Rose, A. Semra, F. Robert
"Resolution and asymmetric synthesis of ortho-substituted benzaldehydetricarbonylchromium complexes"
J. Am. Chem. Soc.1992, 114, 8288-8290.
A. Alexakis, N. Lensen, J.-P. Tranchier, P. Mangeney
"Reactivity and diastereoselectivity of Grignard reagents toward the hydrazone functionality in toluene solvent"
J. Org. Chem.1992, 57, 4563-4565.
A. Alexakis, A.-M. Barthel, J. F. Normant, C. Fugier, M. Leroux
"A new efficient and stereoselective synthesis of 1,3E, 5Z-undecatriene"
Synthetic Communications1992, 22, 1839-1844.
I. Marek, A. Alexakis, P. Mangeney, J. F. Normant
"Synthèse d'alcoxy-allènes chiraux par carbocupration d'acétals propargyliques. Etude de leur réactivité à l'égard d'organocuprates"
Bull. Soc. Chim. Fr.1992, 129, 171-190.
A. Alexakis, S. Mutti, P. Mangeney
"A new reagent for the determination of the optical purity of primary, secondary and tertiary chiral alcohols and of thiols"
J. Org. Chem.1992, 57, 1224-1237.
G. Courtemanche, A. Alexakis, J. Vaissermann, J. F. Normant
"Conjugate addition of organocuprates on γ-methyl-δ-oxy-α,β-enones. Influence of the alkoxy substituent on the diastereoselection"
J. Organomet. Chem.1992, 423, 238-305.
A. Alexakis, S. Mutti, P. Mangeney, J. F. Normant
"A new chiral ligand for the asymmetric conjugate addition of organocopper reagents to enones"
J. Am. Chem. Soc.1991, 113, 6332-6334.
A. Alexakis, N. Lensen, P. Mangeney
"Chiral aminal templates 6. Diastereoselectivity of hydrazo-ne alkylation. Asymmetric synthesis of α-amino-aldehydes"
Tetrahedron Lett.1991, 32, 1171-1174.
A. Alexakis, I. Marek, P. Mangeney, J. F. Normant
"Diastereoselective syn or anti opening of propargylic epoxides. Synthesis of α-allenic alcohols"
Tetrahedron1991, 47, 1677-1696.
R. Gosmini, P. Mangeney, A. Alexakis, M. Commerçon, J. F. Normant
"Chiral aminal templates 5. Preparation of chiral 3-carboxaldehydes-1,4-dihydropyridines"
Synlett1991, 111-113.
A. Alexakis, S. Mutti, J. F. Normant, P. Mangeney
"A new reagent for a very simple and efficient determination of enantiomeric purity of alcohols by 31P NMR"
Tetrahedron: Asymmetry1990, 1, 437-440.
A. Alexakis, I. Marek, P. Mangeney, J. F. Normant
"Mechanistic aspects on the formation of chiral allenes from propargylic ethers and organocopper reagents"
J. Am. Chem. Soc.1990, 112, 8042-8047.
J. F. Normant, J. C. Quirion, Y. Masuda, A. Alexakis
"Reactivity of allyl-zinc (and copper) reagents towards allenic ethers and α-metallated allenic ethers"
Tetrahedron Lett.1990, 31, 2879-2882.
M. Commerçon, P. Mangeney, T. Tejero, A. Alexakis
"Chiral aminal templates 4. Chiral aryl metallic reagents: reactions with aldehydes"
Tetrahedron: Asymmetry1990, 1, 287-289.
A. Alexakis, R. Sedrani, J. F. Normant, P. Mangeney
"Chiral aminal templates 3. Diastereoselectivity of organo-metallic attack on aldehydes bearing a chiral imidazolidine group"
Tetrahedron: Asymmetry1990, 1, 283-286.
A. Alexakis, J. Hanaïzi, D. Jachiet, J. F. Normant
"Unusual 1,2-migration in organoaluminium chemistry, promoted by BF3.OEt2"
Tetrahedron Lett.1990, 31, 1271-1274.
A. Alexakis, R. Sedrani, P. Mangeney
"Stereochemical effects of trimethylsilyl chloride (TMSCl) on the conjugate addition of organocopper reagents"
Tetrahedron Lett.1990, 31, 345-348.
A. Alexakis, D. Jachiet
"A completely stereoselective intramolecular Diels-Alder reaction in the substituted cyclohexanol series"
Tetrahedron1989, 45, 6203-6210.
A. Alexakis, I. Marek, P. Mangeney, J. F. Normant
"Copper catalyzed reductive metallation of a propargylic epoxide to an allenyl lithium reagent"
Tetrahedron Lett.1989, 30, 2391-2392.
A. Alexakis, I. Marek, P. Mangeney, J. F. Normant
"Diastereoselective synthesis of α-allenic alcohols from propargylic epoxides"
Tetrahedron Lett.1989, 30, 2387-2390.
D. Cuvinot, P. Mangeney, A. Alexakis, J. F. Normant, J. P. Lellouche
"Chiral trifluoro diamines as convenient reagents for determining the enantiomeric purity of aldehydes by use of 19F NMR spectroscopy"
J. Org. Chem.1989, 54, 2420-2425.
J. F. Normant, A. Alexakis, A. Ghribi, P. Mangeney
"Boron fluoride promoted cleavage of acetals by organocopper reagents. Application to asymmetric synthesis"
Tetrahedron1989, 45, 507-516.
A. Alexakis, D. Jachiet
"A new approach to conjugate dienes. Synthesis of the pheromones of Lobesia Botrana and Bombyx Mori"
Tetrahedron1989, 45, 381-389.
A. Alexakis, J.-M. Duffault
"The hydroalumination of ω-terbutoxy alkynes an easy access to ω-hydroxy alkenyl iodides. Application to the synthesis of dienic insect pheromone"
Tetrahedron Lett.1988, 29, 6243-6246.
A. Alexakis, R. Sedrani, P. Mangeney, J. F. Normant
"Diastereoselective conjugate addition with acetals, oxazolidines and imidazolidines as chiral auxiliaries"
Tetrahedron Lett.1988, 29, 4411-4414.
A. Alexakis, M. Gardette, S. Colin
"Mild protection and deprotection of alcohols as ter-butyl ethers in the field of pheromone synthesis"
Tetrahedron Lett.1988, 29, 2951-2954.
P. Mangeney, A. Alexakis, J. F. Normant
"Resolution and determination of enantiomeric excesses of chiral aldehydes via chiral imidazolidines"
Tetrahedron Lett.1988, 29, 2677-2680.
P. Mangeney, A. Alexakis, J. F. Normant
"Improved optical resolution of R*,R* N,N'-dimethyl 1,2-diphenyl ethylene diamine"
Tetrahedron Lett.1988, 29, 2675-2676.
C. Fugier, M. Leroux, R. Mauge, A. Alexakis, J. F. Normant
"Nouveau procédé de préparation énantiospécifique du (S) éthylamino-2 (trifluorométhyl-3 phényl)-1 propane"
Brevet d'Invention1988, n° 5614.
P. Mangeney, T. Tejero, A. Alexakis, F. Grosjean, J. F. Normant
"Titanium induced coupling of imines to symmetrical vicinal (R*,R*)-diamines"
Synthesis1988, 255-259.
A. Alexakis, P. Mangeney, A. Ghribi, I. Marek, R. Sedrani, C. Guir, J.-F. Normant
"Chiral acetals in enantio- and diastereoselective substitution or elimination reactions"
Pure Appl. Chem.1988, 60, 49-56.
P. Mangeney, A. Alexakis, J. F. Normant
"Acetals as chiral auxiliaries. Part 4. Asymmetric synthesis of γ,δ-ethylenic aldehydes. An approach to the California Red Scale Pheromone"
Tetrahedron Lett.1987, 28, 2363-2366.
A. Alexakis, D. Jachiet, J. F. Normant
"Boron fluoride promoted opening of epoxides by organocopper or cuprates reagents"
Tetrahedron1986, 42, 5607-5619.
I. Marek, P. Mangeney, A. Alexakis, J. F. Normant
"Are allenes formed from propargylic ethers through a syn or anti displacement α"
Tetrahedron Lett.1986, 27, 5499-5502.
C. Fugier, M. Leroux, J. F. Normant, A. Alexakis
"Nouveau procédé de préparation des undécatriènes-1,3,5"
Brevet d'invention Européen1986, n° 86 107 380.7.
N. Jabri, A. Alexakis, J. F. Normant
"Palladium mediated synthesis of conjugate (E) or (Z) enones and unsymmetrical divinyl ketones. One-pot preparation of Isoegomaketone"
Tetrahedron1986, 42, 1369-1380.
A. Alexakis, J. Berlan, Y. Besace
"Organocopper conjugate addition reaction in the presence of trimethylchlorosilane"
Tetrahedron Lett.1986, 27, 1047-1050.
M. Gardette, A. Alexakis, J. F. Normant
"Alkenyl copper reagents 26. Carbocupration of alkynes by reagents bearing a protected hydroxy or thiol function"
Tetrahedron1985, 41, 5887-5899.
C. Fugier, M. Leroux, J. F. Normant, A. Alexakis
"Nouveau procédé de préparation des undécatriènes"
Brevet d'invention, Institut National de la Propriété Industrielle1985, n° 85 08181.
A. Alexakis, J. F. Normant
"Alkenylcopper Derivatives; 27. Synthesis of 1-Alkenyl Thioethers by Cleavage of Disulfides with 1-Alkenyl-copper Reagents"
Synthesis1985, 72-74.
C. Germon, A. Alexakis, J. F. Normant
"Alkenyl copper derivatives 28. Stereospecific synthesis of tertiary allylic amines of (E) or (Z) configuration"
Bull. Soc. Chim. France II1984, 377-389.
M. Gardette, N. Jabri, A. Alexakis, J. F. Normant
"General methodology for the synthesis of conjugated dienic insect sex pheromones"
Tetrahedron1984, 40, 2741-2750.
A. Alexakis, J. F. Normant
"Alkenyl copper derivatives 25. Synthesis of (E) or (Z) enol ethers by carbocupration of alkoxy-allenes"
Israel J. Chem.1984, 24, 113-117.
A. Ghribi, A. Alexakis, J. F. Normant
"Reactivity of RCu,BF3 and R2CuLi,BF3 toward the ether linkage. Epoxides, acetals and orthoformates"
Tetrahedron Lett.1984, 25, 3075-3078.
P. Mangeney, A. Alexakis, J. F. Normant
"Etude d'un modele d'induction asymetrique: Les oxazolidines α,β-insaturées issues de l'éphédrine"
Tetrahedron1984, 40, 1803-1808.
A. Alexakis, A. Commercon, C. Coulentianos, J. F. Normant
"Alkenyl copper reagents - 18. Carbocupration of acetylenic acetals and ketals. Synthesis of manicone, geranial and 2,4-(E,Z)-dienals"
Tetrahedron1984, 40, 715-731.
G. Friour, A. Alexakis, G. Cahiez, J. Normant
"Reactivity of organomanganese derivatives. VIII. Preparation of ketones by acylation of organomanganese compounds. Effect of acylating agent, solvents, and ligands"
Tetrahedron1984, 40, 683-693.
A. Alexakis, C. Chuit, M. Commercon-Bourgain, J. . P. Foulon, N. Jabri, P. Mangeney, J. F. Normant
"Organocopper reagents for the synthesis of saturated, and a,b-ethylenic aldehydes and ketones"
Pure Appl. Chem.1984, 56, 91-98.
C. Germon, A. Alexakis, J. F. Normant
"Alkenylcopper derivatives; 21. Synthesis of allylic amides and amines by amidomethylation of alkenylcopper and -cuprate reagents"
Synthesis1984, 40-43.
N. Jabri, A. Alexakis, J. F. Normant
"Alkenyl-copper derivatives. 20. Preparation of polysubstituted conjugated dienes by coupling of alkenyl halides with alkenyl copper reagents"
Bull. Chem. Soc. Fr.1983, 332-338.
N. Jabri, A. Alexakis, J. F. Normant
"Alkenyl-copper derivatives. 19. Synthesis of conjugated dienes and styrenes by coupling of alkenyl cuprates with alkenyl and aryl halides"
Bull. Chem. Soc. Fr.1983, 321-331.
F. Scott, B. G. Mafunda, J. F. Normant, A. Alexakis
"Spiroannelation viagem-dihalocyclopropane substrates and a cyclocuprate species"
Tetrahedron Lett.1983, 24, 5767-5770.
N. Jabri, A. Alexakis, J. F. Normant
"Alkenylcopper derivatives. 24. Stereospecific synthesis of enones by palladium-catalyzed acylation of alkenylcopper reagents"
Tetrahedron Lett.1983, 24, 5081-5084.
A. Alexakis, A. Commercon, C. Coulentianos, J. F. Normant
"Carbocupration of acetylenic acetals and ketals: synthesis of α,β ethylenic acetals, and of dienals and dienones"
Pure Appl. Chem.1983, 55, 1759-1766.
J. F. Normant, A. Alexakis
"Preparation of conjugated dienes and enynes via organocopper reagents"
In Transition Metals in Organic Synthesis; R. Scheffold (Ed.); Salle + Sauerlander 5527, John Wiley1983; Vol. 3; p. 139.
M. Gardette, A. Alexakis, J. F. Normant
"Synthesis of (Z,Z)-3,13-octadecadien-1-yl acetate. Component of the sex pheromone of Synanthedon tenuis"
J. Chem. Ecology1983, 9, 225-233.
M. Gardette, A. Alexakis, J. F. Normant
"Synthesis of (Z)-13-Hexadecen-11-yn-1-yl acetate, major component of the sex pheromone of the Processionary moth"
J. Chem. Ecology1983, 9, 219-223.
P. Mangeney, A. Alexakis, J. F. Normant
"Synthèse asymétrique d'aldéhydes à partir d'oxazolidines chirales α,β-insaturées et d'organocuprates"
Tetrahedron Lett.1983, 24, 373-374.
M. Gardette, A. Alexakis, J. F. Normant
"Organocuivreux vinyliques 17. Carbocupration d'alcynes par des organocuprates et cuivreux fonctionnels"
Tetrahedron Lett.1982, 23, 5155-5158.
A. Alexakis, J. F. Normant
"Vinyl-copper reagents 16. Synthesis of conjugated dienes via the addition of vinyl cuprates to acetylene"
Tetrahedron Lett.1982, 23, 5151-5154.
N. Jabri, A. Alexakis, J. F. Normant
"Vinyl-copper derivatives 15. An efficient synthesis of polysubstituted conjugated dienes"
Tetrahedron Lett.1982, 23, 1589-1592.
A. Alexakis
"Réactifs organo-cuivreux : nouveaux agents de synthèse de pheromone sexuelle d'insectes"
In Les mediateurs chimiques agissant sur le comportement des insectes; Les colloques de l'INRA, Vol. 7; 1982; p. 33.
N. Jabri, A. Alexakis, J. F. Normant
"Vinyl-copper derivatives XIII: Synthesis of conjugated dienes of very high stereoisomeric purity"
Tetrahedron Lett.1981, 22, 959-962.
C. Germon, A. Alexakis, J. F. Normant
"Vinyl-copper derivatives. XII. Stereospecific synthesis of allylic amines by aminomethylation of organocopper reagents"
Tetrahedron Lett.1980, 21, 3763-3766.
A. Alexakis, G. Cahiez, J. F. Normant
"Vinylcopper derivatives. XI. Reactivity of Z-alkenylcuprates towards various electrophiles. Application to the synthesis of some natural products"
Tetrahedron1980, 36, 1961-1969.
G. Cahiez, A. Alexakis, J. F. Normant
"Simple stereospecific synthesis of the insect sex pheromones of Cossus cossus, Eupoecilia ambiguella, and Orgyia pseudotsugata"
Tetrahedron Lett.1980, 21, 1433-1436.
J. F. Normant, A. Alexakis, G. Cahiez
"Action d'organolithiens et organomagnésiens sur la propiolactone en présence de sels cuivreux. Synthèse d'acides carboxyliques"
Tetrahedron Lett.1980, 21, 935-938.
A. Alexakis, G. Cahiez, J. F. Normant
"Organocuivreux vinyliques IX. Addition de dérivés organiques du cuivre sur l'acétylène"
J. Organomet. Chem.1979, 177, 293-298.
G. Cahiez, A. Alexakis, J. F. Normant
"Organomanganese(II) reagents. V. Organomanganous chlorides as a new reagent for ketone synthesis via mixed or symmetrical anhydrides"
Synthetic Comm.1979, 9, 639-645.
A. Alexakis, M. J. Chapdelaine, G. H. Posner
"A new approach to the bicyclo[3.2.1]octane ring system: Intramolecular michael and aldol reactions of 3-(5-oxohexyl)-2-cyclopentenones"
Tetrahedron Lett.1978, 19, 4209-4212.
J. F. Normant, T. Mulamba, F. Scott, A. Alexakis, G. Cahiez
"Substitution directe de l'halogène d'halohydrines 1-2 par des organomagnésiens et lithiens en présence de sels cuivreux"
Tetrahedron Lett.1978, 19, 3711-3712.
A. Alexakis, G. Cahiez, J. F. Normant
"Highly stereoselective synthesis of the insect sex pheromone of Phthorimaea operculella and of propylure"
Tetrahedron Lett.1978, 2027-2030.
J. G. Duboudin, B. Jousseaume, A. Alexakis, G. Cahiez, J. Villieras, J. F. Normant
"Addition comparée d'organocuivreux, d'organocuprates et d'organomagnésiens en présence de Cu(I) en quantité catalytique sur l'alcool propargylique"
C. R. Acad. Sc. Paris, Ser. C.1977, 285, 29-31.
G. H. Posner, C. E. Whitten, J. J. Sterling, D. J. Brunelle, C. M. Lentz, A. W. Runquist, A. Alexakis
"New organocopper synthetic methods. α,β-dialkylation of α,β-ethylenic ketones : synthesis of sesquiterpenes"
Ann. New York Acad. Sci.1977, 295, 249-253.
A. Alexakis, G. Cahiez, J. F. Normant, J. Villieras
"Organo-cuivreux vinyliques VIII. Etude de la régio-sélectivité de l'addition des dérivés organo-cuivreux sur les alcynes hétérosubstitués. Utilisation en synthèse des complexes organo-cuivreux obtenus"
Bull. Soc. Chim. Fr.1977, 693-698.
A. Alexakis, J. Normant, J. Villieras
"Dérivés organo-cuivreux vinyliques VII. Addition de l'acétylène sur des cuprates lithiens : synthèse d'homo et d'hétéro-vinyl cuprates lithiens (Z)"
Tetrahedron Lett.1976, 17, 3461-3462.
A. Alexakis, A. Commerçon, J. Villieras, J. F. Normant
"Dérivés organo-cuivreux vinyliques VI. Addition régiosélective d'organocuprates sur des acétals α-acétyléniques. Synthèse d'un acétal du Géranial"
Tetrahedron Lett.1976, 17, 2313-2316.
A. Alexakis
"Etude de la régiosélectivité de l'addition d'organo-cuivreux sur des alcynes fonctionnels"
Thèse de doctorat d'Etat Paris1975, 23 Jan., N° CNRS : AO 12960.
A. Alexakis, J. F. Normant, J. Villieras
"Organo-vinyl-copper compounds V. Regioselectivity in the addition of alkyl-copper-magnesium bromide reagents on various propargyl derivatives"
J. Mol. Catal.1975, 1, 43-58.
A. Alexakis, J. Normant, J. Villieras
"Organocuivreux vinyliques : IV. Etude de la régiosélectivité de l'addition d'un alkyl-cuivre sur des alcynes β et γ fonctionnels"
J. Organomet. Chem.1975, 96, 471-485.
J. F. Normant, A. Alexakis, A. Commercon, G. Cahiez, J. Villieras
"Organo-cuivreux alcoxy et alkylthio-vinyliques : intermédiaires de synthèse d'alcènes hétérosubstitués stéréospécifiquement"
C. R. Acad. Sc. Paris, Ser. C.1974, 279, 763-765.
J. F. Normant, G. Cahiez, C. Chuit, A. Alexakis, J. Villieras
"Synthèse stéréospécifique d'oléfines di- et trisubstituées par alcoylation des vinyl cuivres"
J. Organomet. Chem.1972, 40, C49-C52.
texe intégral
