Ni-Catalyzed Regioselective 1,2-Dicarbofunctionalization of Olefins by Intercepting Heck Intermediates as Imine-Stabilized Transient Metallacycles
Ni-Catalyzed Regioselective 1,2-Dicarbofunctionalization of Olefins by Intercepting Heck Intermediates as Imine-Stabilized Transient Metallacycles
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DOI：
10.1021/jacs.7b06340
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发表时间：
2017-08-09
影响因子：
15
通讯作者：
Giri, Ramesh
中科院分区：
文献类型：
--
作者：
Shrestha, Bijay;Basnet, Prakash;Giri, Ramesh
我们公开了一种通过用芳基锌试剂拦截Heck C（sp（3））-NiX中间体来进行Ni催化的苯乙烯中的烯烃的双碳官能化的策略。该方法利用容易去除的亚胺作为配位基团，其起到双重作用，即拦截衍生自芳基卤化物和三氟甲磺酸酯的氧化加成物质以促进Heck碳化和稳定Heck C（sp（3））-NiX中间体作为瞬时金属杂环以抑制β-氢化物消除并促进金属转移/还原消除步骤。该方法提供了在各种天然产物中作为结构基序出现的二硫代取代的1，1，2-三芳基乙基产物。
We disclose a strategy for Ni-catalyzed dicarbofunctionalization of olefins in styrenes by intercepting Heck C(sp(3))-NiX intermediates with arylzinc reagents. This approach utilizes a readily removable imine as a coordinating group that plays a dual role of intercepting oxidative addition species derived from aryl halides and triflates to promote Heck carbometalation and stabilizing the Heck C(sp(3))-NiX intermediates as transient metallacycles to suppress beta-hydride elimination and facilitate transmetalation/reductive elimination steps. This method affords diversely substituted 1,1,2-triarylethyl products that occur as structural motifs in various natural products.