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镍催化的全氟烯烃与非活化仲烷基和叔烷基卤化物的脱氟还原交叉偶联反应。

Nickel-Catalyzed Defluorinative Reductive Cross-Coupling of gem-Difluoroalkenes with Unactivated Secondary and Tertiary Alkyl Halides.

机构信息

Hefei National Laboratory for Physical Sciences at the Microscale, CAS Key Laboratory of Urban Pollutant Conversion, Anhui Province Key Laboratory of Biomass Clean Energy, iChEM, University of Science and Technology of China , Hefei 230026, China.

出版信息

J Am Chem Soc. 2017 Sep 13;139(36):12632-12637. doi: 10.1021/jacs.7b06469. Epub 2017 Aug 29.

DOI:10.1021/jacs.7b06469
PMID:28849923
Abstract

Herein, we described a nickel-catalyzed monofluoroalkenylation through defluorinative reductive cross-coupling of gem-difluoroalkenes with alkyl halides. Key to the success of this strategy is the combination of C-F cleavage with alkyl halides activation. This reaction enables the convenient synthesis of a large variety of functionalized monofluoroalkenes under mild reaction conditions with broad functional group compatibility and excellent Z-selectivity. The combination of Ni catalysis with (Bpin)/KPO as terminal reductant promoted the efficient C(sp)-C(sp) formation especially the generation of all-carbon quaternary centers with high chemoselectivity.

摘要

在此,我们描述了一种镍催化的单氟烯基化反应,通过二氟烯与卤代烷烃的脱氟还原交叉偶联来实现。该策略的关键在于 C-F 键的断裂与卤代烷烃的活化相结合。在温和的反应条件下,该反应具有广泛的官能团兼容性和优异的 Z 选择性,能够方便地合成各种官能化的单氟烯。Ni 催化与(Bpin)/KPO 作为末端还原剂的结合促进了高效的 C(sp)-C(sp) 形成,特别是具有高化学选择性的全碳季碳中心的生成。

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