A Remarkable Switch from a Diamination to a Hydrohydrazination Catalyst and Observation of an Unprecedented Catalyst Resting State
作者:Andrew D. Schwarz、Chee S. Onn、Philip Mountford
DOI:10.1002/anie.201206249
日期:2012.12.3
alkynes gave the unusual acetylide–vinylhydrazide(1−) compounds 2 (R=4‐C6H4X (X=Me, CF3, OMe), C6F5, SiMe3) as hydrohydrazination intermediates. In contrast, a complex similar to 1 with bulkier trimethylsilyl substituents in place of the isopropyl groups is known to catalyze the 1,2‐diamination of alkynes with hydrazines.
很小的变化带来的巨大影响:钛配合物1与末端炔烃的反应产生了不寻常的乙炔-乙烯基酰肼(1-)化合物2(R = 4-C 6 H 4 X(X = Me,CF 3,OMe), C 6 F 5,SiMe 3)作为氢化肼化中间体。相反,已知一种类似于1的配合物,具有更大的三甲基甲硅烷基取代基来代替异丙基,可以催化炔类与肼的1,2-重整反应。