过渡金属催化氯代物的羰基化反应研究进展

Recent advances on transition metal catalyzed carbonylation of chlorinated compounds

有机氯代物相对于溴代物和碘代物价格低廉且储量丰富,其通过羰基化反应合成的下游产品醛、羧酸、酰胺、酯在大宗化学品、精细化学品以及医药中间体等的生产上有重要应用。本文综合评述了氯代物羰基化反应合成高附加值化学品的重要性,介绍了几种不同类型的氯代物(芳基氯代物、烯丙基氯代物、苄基氯代物、α-氯代酮、1,1-二氯-1-乙烯基化合物、烷基氯代物)羰基化反应(甲酰化反应、酯化反应、酰胺化反应和羧化反应等)在发展新型催化剂体系及高效合成目标产物方面的研究进展,并对该类底物羰基化反应存在的难点以及未来发展方向进行了展望。未来发现更多类型的反应和催化剂体系,实现氯代物的温和羰基化是有机化学研究以及工业化生产的难题及热点。

Compared with brominated and iodinated substitutes,chlorinated substitutes are cheaper and more abundant in reserves.The downstream products such as aldehydes,carboxylic acids,amides and esters synthesized by carbonylation reaction have important applications in the production of bulk chemicals,fine chemicals and pharmaceutical intermediates.This paper comprehensively reviews the importance of chlorinated compounds carbonylation to synthesize high value-added chemicals,and introduces the research progress of several different types of chlorinated compounds(aryl chlorinated compounds,allyl chlorinated compounds,benzyl chlorinated compounds,α-chlorinated ketones,1,1-dichloro-1-vinyl compounds,alkyl chlorides)and their carbonylation reactions(formylation,esterification,amination,carboxylation,etc.)in the development of new catalyst systems and efficient synthesis of target products.The difficulties and future development of carbonylation of such substrates are also prospected.In the future,the development of more types of reactions and catalyst systems that accomplish the mild carbonylation of chlorinated compounds would be a hot spot in organic chemistry research and industrial production.