Soriano Elena, Ballesteros Paloma, Marco-Contelles José
Sección de Síntesis Orgánica e Imagen Molecular por Resonancia Magnética, Instituto Universitario de Investigación, UNED, c/Senda del Rey 9, Madrid 28040, Spain.
J Org Chem. 2004 Nov 12;69(23):8018-23. doi: 10.1021/jo048828h.
A mechanistic study based on DFT theoretical calculations for the PtCl(2)-catalyzed formation of bicyclic adducts from heteroatom tethered 1,6-enynes is reported. Different reaction pathways have been taken into account and the results are discussed. This analysis clearly reveals that the kinetically preferred pathway involves an initial 6-endo-cyclization from a triggered reactant complex by pi-complexation of Pt(II) onto the alkyne to form a cyclopropyl platina-carbene intermediate, followed by a [1,2]-hydrogen shift.
报道了一项基于密度泛函理论（DFT）计算的机理研究，该研究针对PtCl(2)催化由杂原子连接的1,6-烯炔形成双环加合物的反应。考虑了不同的反应途径并对结果进行了讨论。该分析清楚地表明，动力学上优先的途径涉及由Pt(II)与炔烃通过π-络合作用引发反应物络合物进行初始的6-内型环化，以形成环丙基铂卡宾中间体，随后进行[1,2]-氢迁移。
