Department of Chemistry, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China.
Chemistry. 2018 Jul 11;24(39):9760-9764. doi: 10.1002/chem.201801448. Epub 2018 Jun 7.
The first examples of C-C bond cleavage reactions of internal propargyl alcohols to give vinylidene complexes are described. Treatment of [Re(dppm) ]I with RC≡CC(OH)R'R'' (R=aryl, alkyl; C(OH)R'R''=C(OH)Ph C(OH)Me , C(OH)HPh, C(OH)H ) produced the vinylidene complexes ReI(=C=CHR)(dppm) with the elimination of C(O)R'R''. Computational studies support that the reactions proceed through a β-alkynyl elimination of alkoxide intermediates Re{OC(R')(R'')C≡CR}(dppm) .
首次描述了内部炔丙醇的 C-C 键断裂反应，生成了亚乙烯基配合物。[Re(dppm)]I 与 RC≡CC(OH)R'R''（R=芳基，烷基；C(OH)R'R''=C(OH)Ph、C(OH)Me、C(OH)HPh、C(OH)H）反应，生成了亚乙烯基配合物 ReI(=C=CHR)(dppm)，同时消除了 C(O)R'R''。计算研究支持反应通过β-炔基消除醇盐中间体 Re{OC(R')(R'')C≡CR}(dppm)进行。
