常温常压下光促进烯烃与一氧化碳的羰基化反应

 报道了烯烃（环己烯和1－辛烯）与一氧化碳通过光促进实现常温常压非贵金属（钴配合物）催化的羰基化反应．研究发现，以Co（OAc）2为催化剂时，不需要加入光敏剂丙酮就能发生反应；CoSalen，吡啶－2－羧酸钴和大环配合物［Co（14）4，11－diene－N4］I2是较好的催化剂，其催化活性比Co（OAc）2高．其中，吡啶－2－羧酸钴与Co（OAc）2相同，反应中不需要光敏剂存在，其选择性很高．通过氘代丙酮和氘代甲醇同位素实验，进一步证实了反应中双键异构的存在和副产物的分析结果．

Photopromoted Carbonylation of Olefins and Carbon Monoxide under Ambient Conditions

Photopromoted carbonylation of olefins and CO under ambient conditions is a promising reaction to be used as an environmentally friendly technique. A typical procedure is as follows: a quartz tube containing substrate and catalyst in CH 3OH CH 3COCH 3 solution (volume ratio=3) was irradiated by a high pressure mercury lamp of 400 W at RT under atmospheric pressure of CO. It was found that the carbonylation occurred even without addition of acetone when using Co(OAc) 2 as catalyst. Under the catalysis of Co(OAc) 2, the yields of esters in the carbonylation of cyclohexene without or with addition of acetone were 70% and 63% respectively, meanig that acetone is not the key factor to determine the photopromoted carbonylation. The exactly same results could be got in the carbonylation of 1 octene. Several other cobalt complexes, such as CoSalen, cobalt picolinic ester and Co(14)4,11 diene N 4]I 2, were synthesized and studied. The yields of esters formed from cyclohexene were 48%, 45% and 55% respectively, and the catalytic activity of the cobalt complexes was higher than that of Co(OAc) 2. It was also found that no carbonylation took place without addition of acetone when catalyzed by CoSalen, just like in catalysis of Co(acac) 2. By contrast, the carbonylation did take place without acetone under the circumstance of both cobalt picolinic ester and Co(OAc) 2. In catalysis of Co(14)4,11 diene N 4]I 2, the reaction could proceed with or without addition of acetone, and a much higher yield was obtained by addition of acetone. The carbonylation of cyclohexene gave the product cyclo C 6H 11 COOCH 3 without D in it when using CD 3COCD 3 instead of CH 3COCH 3, supporting the hypothesis that CH 3 and H in the product can come from methanol. When using CD 3OD instead of CH 3OH, there were the products cyclo C 6H 10 D COOCD 3 and cyclo C 6H 9D 2 COOCD 3, explaining the double bond shift during the carbonylation.