Tenaglia Alphonse, Marc Sylvain
Laboratoire de Synthèse Asymétrique, UMR CNRS 6180, Université Paul Cézanne, EGIM Sud, Av. Escadrille Normandie Niemen, F-13397 Marseille Cedex 20, France.
J Org Chem. 2006 Apr 28;71(9):3569-75. doi: 10.1021/jo060276a.
The electron-rich cyclopentadienylruthenium complex CpRuCl(PPh3)2 turns out to be an efficient catalyst for the regio- and stereoselective cyclopropanation of bicyclic alkenes with tertiary propargylic carboxylates. The reaction provides 1,2,3-trisubstituted cyclopropanes in high yields as a single stereoisomer instead of the expected cyclobutenes via [2 + 2] cycloaddition. Functional groups such as ethers, esters, alcohols, phenols, ketones, esters, carboxylic anhydrides, nitriles, halides, sulfones, imides, carbamates, and azines are tolerated with the catalyzed reaction. An efficient cyclopropanation of cyclobutenes was also demonstrated, providing the strained bicyclo[2.1.0(1,3)]pentane framework.
富电子的环戊二烯基钌配合物CpRuCl(PPh₃)₂被证明是一种高效催化剂，可用于双环烯烃与叔炔丙基羧酸盐的区域和立体选择性环丙烷化反应。该反应通过[2 + 2]环加成反应，以高收率提供单一立体异构体的1,2,3-三取代环丙烷，而不是预期的环丁烯。醚、酯、醇、酚、酮、酯、羧酸酐、腈、卤化物、砜、酰亚胺、氨基甲酸酯和吖嗪等官能团在催化反应中均能耐受。还证明了环丁烯的高效环丙烷化反应，可提供具有张力的双环[2.1.0(1,3)]戊烷骨架。
