Gulías Moisés, García Rebeca, Delgado Alejandro, Castedo Luis, Mascareñas José L
Departamento de Química Orgánica y Unidad Asociada al CSIC, Universidad de Santiago de Compostela, Spain.
J Am Chem Soc. 2006 Jan 18;128(2):384-5. doi: 10.1021/ja054487t.
Readily accessible alk-5-enylidenecyclopropanes undergo [3 + 2] intramolecular cycloaddition reactions upon treatment with appropriate palladium complexes. The method allows the rapid and efficient assembly of a variety of bicyclo[3.3.0]octane systems with up to three stereocenters. Preliminary theoretical calculations uncovered previously unsuspected mechanistic possibilities based on either a concerted pallada-ene-like rearrangement or a stepwise process involving zwitterionic intermediates.
易于获得的烯基-5-亚烷基环丙烷在用适当的钯配合物处理时会发生[3 + 2]分子内环加成反应。该方法能够快速有效地构建各种具有多达三个立体中心的双环[3.3.0]辛烷体系。初步的理论计算揭示了基于协同的类钯烯重排或涉及两性离子中间体的逐步过程的前所未有的机理可能性。
