Copper-Catalyzed Asymmetric Defluoroborylation of 1-(Trifluoromethyl)Alkenes
Copper-Catalyzed Asymmetric Defluoroborylation of 1-(Trifluoromethyl)Alkenes
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DOI：
10.1016/j.chempr.2018.07.003
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发表时间：
2018-09-13
期刊：
影响因子：
23.5
通讯作者：
Shi, Zhuangzhi
中科院分区：
文献类型：
--
作者：
Gao, Pan;Yuan, Chengkai;Shi, Zhuangzhi
宝石-二氟烯烃具有类似于酮类、醛类和酯类的立体和电子构型，因此在现代药物发现中被广泛用作羰基同位异构体。虽然为获得宝石-二氟烯烃已作了许多尝试，但在宝石-二氟乙烯基的a位上诱导对映体选择性仍然是一个挑战。本文描述了一种通过铜催化的1-（三氟甲基）烯烃与B(2)销(2)的去氟硼化反应，构建具有高对映体过量的宝石-二氟烯基硼酸盐的有效方法。反应条件温和，各种常见的官能团，如醚、氟、氯、溴、碘、酯、氰基、硫化物、氨基和吲哚基都能很好地耐受。此外，我们不仅将该系统作为复杂化合物后期修饰的强大合成工具，而且还强调了形成的化合物在合成中的实用性。
gem-Difluoroalkenes have steric and electronic profiles similar to those of ketones, aldehydes, and esters, and consequently have been used widely as carbonyl isosteres in modern drug discovery. Although many attempts have been made to achieve gem-difluoroalkenes, the induction of enantioselectivity at the a position of a gem-difluorovinyl group still remains a challenge. Herein, an efficient method for the construction of gem-difluoroallylboronates with high enantiomeric excess via a copper-catalyzed defluoroborylation of 1-(trifluoromethyl) alkenes with B(2)pin(2) is described. The reaction conditions were mild, and a variety of common functional groups, such as ether, fluoride, chloride, bromide, iodide, ester, cyano, sulfide, amino, and indoyl groups, were well tolerated. Furthermore, we not only applied this developed system as a powerful synthetic tool for the late-stage modification of complex compounds but also highlighted the utility of the formed compounds in synthesis.