TY - JOUR AU - Li, Hailing AU - Grassi, David AU - Guénée, Laure AU - Bürgi, Thomas AU - Alexakis, Alexandre TI - Copper-Catalyzed Propargylic Substitution of Dichloro Substrates: Enantioselective Synthesis of Trisubstituted Allenes and Formation of Propargylic Quaternary Stereogenic Centers PY - 2014 JF - Chemistry - A European Journal JA - Chem. - Eur. J. SN - 0947-6539 VL - 20 IS - 50 SP - 16694 EP - 16706 L1 - http://onlinelibrary.wiley.com/doi/10.1002/chem.201404668/pdf L2 - http://onlinelibrary.wiley.com/enhanced/doi/10.1002/chem.201404668 L3 - http://doi.wiley.com/10.1002/chem.201404668 M3 - 10.1002/chem.201404668 UR - http://dx.doi.org/10.1002/chem.201404668 KW - allenes KW - asymmetric catalysis KW - copper KW - Grignard reagents KW - P ligands N2 - An easy and versatile Cu-catalyzed propargylic substitution process is presented. Using easily prepared prochiral dichloro substrates, readily available Grignard reagents together with catalytic amount of copper salt and chiral ligand, we accessed a range of synthetically interesting trisubstituted chloroallenes. Substrate scope and nucleophile scope are broad, providing generally high enantioselectivity for the desired 1,3-substitution products. The enantioenriched chloroallenes could be further transformed into the corresponding trisubstituted allenes or terminal alkynes bearing all-carbon quaternary stereogenic centers, through the copper-catalyzed enantiospecific 1,1/1,3-substitutions. The two successive copper-catalyzed reactions could be eventually combined into a one-pot procedure and different desired allenes or alkynes were obtained respectively with high enantiomeric excesses. ID - 1442 ER -