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Organocatalytic Enantioselective Vinylcyclopropane-Cyclopentene (VCP-CP) Rearrangement |
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| Authors: | Gorka Garay Josebe Hurtado Manuel Pedrón Lorena García Dr. Efraim Reyes Eduardo Sánchez-Díez Prof. Dr. Tomás Tejero Prof. Dr. Luisa Carrillo Prof. Dr. Pedro Merino Prof. Dr. Jose L. Vicario |
| Affiliation: | 1. Department of Organic and Inorganic Chemistry, University of the Basque Country (UPV/EHU), P.O. Box 644, 48080 Bilbao, Spain;2. Instituto de Biocomputación y Física de Sistemas Complejos (BIFI), Universidad de Zaragoza, 50009 Zaragoza, Spain;3. Department of Organic and Inorganic Chemistry, University of the Basque Country (UPV/EHU), P.O. Box 644, 48080 Bilbao, Spain Current Address: Centre for Cooperative Research on Alternative Energies (CIC Energigune), Basque Research and Technology Alliance (BRTA), Alava Technology Park, Vitoria-Gasteiz, Spain;4. Instituto de Síntesis Química y Catálisis Homogénea (ISQH), Universidad de Zaragoza CSIC, 50009 Zaragoza, Spain |
| Abstract: | We have demonstrated that the catalytic and enantioselective vinylcyclopropane-cyclopentene rearrangement can be carried out on (vinylcyclopropyl)acetaldehydes through activation via enamine intermediates. The reaction makes use of racemic starting materials that, upon ring opening facilitated by the catalytic generation of a donor-acceptor cyclopropane, deliver an acyclic iminium ion/dienolate intermediate in which all stereochemical information has been deleted. The final cyclization step forms the rearrangement product, showing that chirality transfer from the catalyst to the final compound is highly effective and leads to the stereocontrolled formation of a variety of structurally different cyclopentenes. |
| Keywords: | Asymmetric Catalysis Cyclopropanes DYKAT Organocatalysis Rearrangement |