低温固相でのカルベンの反応

概要

論文の詳細を見る
Reactions of carbenes generated photolytically in rigid organic solid at low temperature are reviewed mainly from the synthetic point of view. In the case of carbenes with triplet ground states there are profound differences between the chemistry observed in fluid solution at ambient temperature and that obtained in matrix at -196°C. For example, the arylcarbene generated in alcoholic solution at ambient temperature gives O-H insertion products almost exclusively, whereas the arylcarbene generated in alcoholic matrices at -196°C results in a dramatic increase in C-H insertion products at the expense of the ether. Similar dependence of the product distributions has been observed in the reaction of the arylcarbene with alkene, amine, halide, ether and acetone. These C-H insertion products are explained to be formed via H atom tunneling from organic solid to the triplet state of arylcarbene, followed by an efficient recombination of the resulting radical pairs. Reactions of arylcarbene with organic compounds with no active C-H bonds, e.g., styrene and t-butyl alcohol are also reviewed.
社団法人有機合成化学協会の論文