International Research Center for Elements Sciencem Institute for Chemical Research (ICR), Kyoto University, Uji, Kyoto, 611-0011, Japan.
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto, 615-8510, Japan.
Angew Chem Int Ed Engl. 2017 Oct 16;56(43):13298-13301. doi: 10.1002/anie.201706333. Epub 2017 Sep 19.
Reported is the anti-selective carbosilylation of internal alkynes with silylborane and alkyl halides using a FeBr /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.
报道了一种使用 FeBr/DPPE 催化剂体系的硅基硼烷与卤代烃对内炔的反选择性碳硅化反应。铁催化剂允许碳亲电试剂和硅亲核试剂同时引入到简单的内炔中，包括二芳基、二烷基和芳基/烷基取代的炔烃，具有高度的立体选择性。卤代烃可用作亲电试剂，从而能够合成各种四取代的烯基硅烷。此外，通过使用硅基上带有氧官能团的硅基硼烷进行立体开关，可以实现 syn-选择性碳硅化反应。这种新型的铁催化碳硅化反应是快速合成立体定义的多取代烯烃的有用工具，烯烃是有机化学中的基本结构单元。
