Catalytic domino reaction of ketones/aldehydes with Me3SiCF2Br for the synthesis of α-fluoroenones/α-fluoroenals.
Catalytic domino reaction of ketones/aldehydes with Me3SiCF2Br for the synthesis of α-fluoroenones/α-fluoroenals.
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DOI：
10.1021/acs.orglett.5b00488
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发表时间：
2015-03
期刊：
影响因子：
5.2
通讯作者：
Xiaoning Song;Jian Chang;Dongsheng Zhu;Jiaheng Li;Cong Xu;Qun Liu;Mang Wang
中科院分区：
文献类型：
--
作者：
Xiaoning Song;Jian Chang;Dongsheng Zhu;Jiaheng Li;Cong Xu;Qun Liu;Mang Wang
本文报道了可烯醇化羰基化合物与Me 3SiCF 2Br反应生成α-氟烯酮和α-氟烯醛的独特的多米诺反应，该反应经历了原位生成二氟卡宾和硅烯醇醚、二氟环丙烷化、脱硅、开环和脱硅等步骤。在该串联反应中，Me 3SiCF 2Br不仅充当二氟卡宾源，而且充当TMS转移剂以及内部溴化物和氟化物阴离子催化剂。它允许的转化下，只有催化量的n-Bu 4 NBr作为引发剂顺利发生。
A unique domino reaction of enolizable carbonyl compounds with Me3SiCF2Br to construct α-fluoroenones and α-fluoroenals is described to undergo the in situ formation of difluorocarbene and silyl enol ether, difluorocyclopropanation, desilylation, ring-opening, and defluorination sequence. In this tandem reaction, Me3SiCF2Br acts as not only the difluorocarbene source but also the TMS transfer agent as well as internal bromide and fluoride anion catalyst. It allows the transformations to occur smoothly under only a catalytic amount of n-Bu4NBr as initiator.