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首页> 外文期刊>Chemistry: A European journal >NHC-Copper(I) Halide-Catalyzed Direct Alkynylation of Trifluoromethyl Ketones on Water
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NHC-Copper(I) Halide-Catalyzed Direct Alkynylation of Trifluoromethyl Ketones on Water

机译：NHC-铜（I）卤化物催化的三氟甲基酮在水中的直接烷基化

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摘要

An efficient and easily scalable NHC-copper(I) halide-catalyzed addition of terminal alkynes to 1,1,1-tri-fluoromethyl ketones, carried out on water for the first time, is reported. A series of addition reactions were performed with as little as 0.1-2.0 mol% of [(NHC)CuX] (X = Cl, Br, I, OAc, OTf) complexes, providing tertiary propargylic trifluoromethyl alcohols in high yields and with excellent chemoselectivity from a broad range of aryl-and more challenging alkyl-substituted trifluoromethyl ketones (TFMKs). DFT calculations were performed to rationalize the correlation between the yield of catalytic alkynylation and the sterics of N-heterocyclic carbenes (NHCs), expressed as buried volume (%VBur), indicating that steric effects dominate the yield of the reaction. Additional DFT calculations shed some light on the differential reactivity of [(NHC)CuX] complexes in the alkynylation of TFMKs. The first enantioselective version of a direct alkynylation in the presence of C-1-symmetric NHC-copper(I) complexes is also presented.
机译：据报道，第一次在水上进行的高效，易扩展的NHC-铜（I）卤化物催化的末端炔烃加成到1,1,1-三氟甲基酮中。使用低至0.1-2.0 mol％的[（NHC）CuX]（X = Cl，Br，I，OAc，OTf）配合物进行一系列加成反应，可高产率提供叔炔丙基三氟甲醇，并具有出色的化学选择性广泛的芳基和更具挑战性的烷基取代的三氟甲基酮（TFMK）。进行DFT计算以合理化催化炔基化收率与N-杂环卡宾（NHC）的空间之间的相关性，用掩埋体积（％VBur）表示，表明空间效应支配了反应的产率。额外的DFT计算为TFMK烷基化中[（NHC）CuX]配合物的差异反应性提供了一些启示。还介绍了在C-1-对称NHC-铜（I）配合物存在下直接炔基化的第一个对映体选择性形式。

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