Department of Organic and Inorganic Chemistry, University of the Basque Country (UPV/EHU), P.O. Box 644, 48080, Bilbao, Spain.
Instituto de Biocomputación y Física de Sistemas Complejos (BIFI), Universidad de Zaragoza, 50009, Zaragoza, Spain.
Angew Chem Int Ed Engl. 2023 May 22;62(22):e202302416. doi: 10.1002/anie.202302416. Epub 2023 Apr 24.
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.
我们已经证明，通过烯胺中间体的活化，可以在（乙烯基环丙基）乙醛醛上进行催化和对映选择性的乙烯基环丙烷-环戊烯重排反应。该反应利用外消旋起始原料，通过催化生成给体-受体环丙烷促进环开裂，生成无环亚氨基离子/二烯醇化物中间体，其中所有立体化学信息都被删除。最后环化步骤形成重排产物，表明手性从催化剂转移到最终化合物是非常有效的，并导致各种结构不同的环戊烯的立体控制形成。
