TY - JOUR AU - Achard, Thierry AU - Tortoreto, Cecilia AU - Poblador-Bahamonde, Amalia I. AU - Guénée, Laure AU - Bürgi, Thomas AU - Lacour, Jérôme TI - [CpRu]-Catalyzed Carbene Insertions into Epoxides: 1,4-Dioxene Synthesis through SN1-Like Chemistry with Retention of Configuration PY - 2014 JF - Angewandte Chemie International Edition JA - Angew. Chem. Intl. Ed. SN - 1433-7851 VL - 53 IS - 24 SP - 6140 EP - 6144 L1 - http://onlinelibrary.wiley.com/doi/10.1002/anie.201402994/pdf L2 - http://onlinelibrary.wiley.com/enhanced/doi/10.1002/anie.201402994 L3 - http://doi.wiley.com/10.1002/anie.201402994 L4 - http://www.unige.ch/sciences/chifi/publis/pics/double/ref01404.png M3 - 10.1002/anie.201402994 UR - http://dx.doi.org/10.1002/anie.201402994 N2 - Rather than lead to the usual deoxygenation pathway, metal carbenes derived from α-diazo-β-ketoesters undergo three-atom insertions into epoxides using a combination of 1,10-phenanthroline and [CpRu(CH3CN)3][BArF] as the catalyst. Original 1,4-dioxene motifs are obtained as single regio- and stereoisomers. A perfect syn stereochemistry (retention, e.r. up to 97:3) is observed for the ring opening, which behaves as an SN1-like transformation. ID - 1404 ER -