布朗斯特酸催化的炔丙基硅烷中的1,2-硅基迁移：甲硅烷基二烯和甲硅烷基茚的合成
Brønsted Acid Catalyzed 1,2-Silyl Shift in Propargyl Silanes: Synthesis of Silyl Dienes and Silyl Indenes.
作者信息
Puriņš Mikus, Mishnev Anatoly, Turks Ma Ris
机构信息
Institute of Technology of Organic Chemistry, Faculty of Materials Science and Applied Chemistry , Riga Technical University , Paula Valdena str. 3 , Riga LV-1048 , Latvia.
Latvian Institute of Organic Synthesis , Aizkraukles 21 , Riga LV-1006 , Latvia.
出版信息
J Org Chem. 2019 Mar 15;84(6):3595-3611. doi: 10.1021/acs.joc.8b02735. Epub 2019 Feb 27.
A general method for generation of allyl carbenium ions from propargyl silanes via a 1,2-silyl shift by Brønsted acids is reported. Two possible reaction pathways are described. Deprotonation results in silyl dienes with yields from 52% to 92%. Intramolecular Friedel-Crafts reactions of aryl-substituted systems give access to silyl indenes with yields of 18-90% depending on the substitution pattern. The obtained products have been shown to react as alkenyl silanes in Hiyama coupling and electrophilic substitution and as dienes in Diels-Alder cycloaddition.
报道了一种通过布朗斯特酸经由1,2-硅基迁移从炔丙基硅烷生成烯丙基碳正离子的通用方法。描述了两种可能的反应途径。去质子化产生硅基二烯，产率为52%至92%。芳基取代体系的分子内傅克反应可得到硅基茚，产率取决于取代模式，为18 - 90%。已证明所得到的产物在日山偶联和亲电取代反应中可作为烯基硅烷反应，在狄尔斯-阿尔德环加成反应中可作为二烯反应。
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