Synthesis and Reactions of Cyclic Silylboranes
Synthesis and Reactions of Cyclic Silylboranes
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DOI：
10.1246/bcsj.78.323
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发表时间：
2005-02
影响因子：
4
通讯作者：
M. Suginome;H. Noguchi;Tomoaki Hasui;M. Murakami
中科院分区：
文献类型：
--
作者：
M. Suginome;H. Noguchi;Tomoaki Hasui;M. Murakami
通过与2-(diisopropylamino)-1，1-diorgano-1-sila-2-boracyclopentanes，形成分子内还原的B-Si键，合成了五元环硅硼烷3-[chloro(diisopropylamino)boryl]-1-(chlorodiorganosilyl)-propane.环状硅基硼烷具有热稳定性，可以在真空下蒸馏。环状硅烷与醇的反应导致硅-B键断裂，而与仲胺的反应导致硼原子上的氨基交换。钯催化剂能有效地催化炔烃插入到环硅基硼烷的Si-B键上，高产率地区域选择性地形成七元环烯烃。
Five-membered cyclic silylboranes, 2-(diisopropylamino)-1,1-diorgano-1-sila-2-boracyclopentanes, were synthesized via intramolecular reductive B-Si bond formation with 3-[chloro(diisopropylamino)boryl]-1-(chlorodiorganosilyl)-propane. The cyclic silylboranes were thermally stable and could be distilled under a vacuum. The reaction of the cyclic silylboranes with alcohols resulted in a cleavage of the Si-B bond, whereas a reaction with sec-amines led to an amino group exchange on the boron atom. The insertion of alkynes into the Si-B bond of the cyclic silylborane was effectively catalyzed by palladium catalysts, leading to a regioselective formation of seven-membered cyclic alkenes in high yields.