Iron-Catalyzed anti-Selective Carbosilylation of Internal Alkynes
Iron-Catalyzed anti-Selective Carbosilylation of Internal Alkynes
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DOI：
10.1002/anie.201706333
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发表时间：
2017-10-16
影响因子：
16.6
通讯作者：
Nakamura, Masaharu
中科院分区：
文献类型：
--
作者：
Iwamoto, Takahiro;Nishikori, Tatsushi;Nakamura, Masaharu
报道了在FeBr 2/DPPE催化体系中，内炔与甲硅烷基硼烷和卤代烷的反选择性羰基化反应。铁催化剂允许以高度立体选择性的方式将碳亲电试剂和硅亲核试剂同时引入简单的内部炔，包括二芳基-、二烷基-和芳基/烷基-取代的炔。烷基卤化物可用作亲电试剂，从而能够合成各种四取代的烯基硅烷。此外，通过使用在甲硅烷基上具有氧官能团的甲硅烷基硼烷，通过立体转换实现顺式选择性甲硅烷基化。这种新型的铁催化的硅碳加成反应是快速合成立体定向多取代烯烃（有机化学中的基本结构基序）的有用工具。
Reported is the anti-selective carbosilylation of internal alkynes with silylborane and alkyl halides using a FeBr2/DPPE catalyst system. The iron catalyst allows simultaneous introduction of a carbon electrophile and a silicon nucleophile to simple internal alkynes, including diaryl-, dialkyl-, and aryl/alkyl-substituted alkynes, in a highly stereoselective manner. Alkyl halides are applicable as the electrophiles, thereby enabling the synthesis of a variety of tetrasubstituted alkenylsilanes. In addition, syn-selective carbosilylation was achieved through stereoswitching, by using a silylborane having oxygen functionality on the silyl group. This novel iron-catalyzed carbosilylation is a useful tool for expedient synthesis of stereodefined multisubstituted olefins, a fundamental structural motif in organic chemistry.