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首页> 外文期刊>European journal of organic chemistry >A route to 2-alkenyl-3-(tert-butyldiphenylsilyl)amines and application to the construction of a tricyclic ring system
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A route to 2-alkenyl-3-(tert-butyldiphenylsilyl)amines and application to the construction of a tricyclic ring system

机译:2-烯基-3-(叔丁基二苯基甲硅烷基)胺的途径及其在三环体系构建中的应用

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摘要

N-Tosyl 3,3-dialkyl-2-(tert-butyldiphenylsilylmethyl)azetidines rearrange smoothly into the corresponding 2-alkenyl-3-(tert-butyldiphenylsilyl)amines upon exposure to BF_3·OEt_2 in CH_2Cl _2. The reaction involves sequential ~σC-N bond cleavage, 1,2-migration of the N-tosyl-aminomethyl group, and deprotonation of the resultant tert-carbenium ions. For the instance in which the carbenium ion formed from migration of the N-tosyl-aminomethyl group is highly stable by virtue of being, for example, tertiary as well as benzylic, the migration takes place in sync with σ_(C-N) bond cleavage, which leads to high configurational control at the tert-butyldiphenylsilylmethyl-bearing carbon atom in the product. In contrast to N-tosyl-substituted 3-alkyl-2-(tert- butyldiphenylsilylmethyl)azetidine, the corresponding 3,3-dialkyl derivative rearranges into N-tosyl-2-alkenyl-3-(tert-butyldiphenylsilyl)amine upon exposure to BF_3·OEt_2. The reaction involves sequential σ_(C-N) bond cleavage, 1,2-migration of the N-tosyl-aminomethyl group, and deprotonation of the resultant tert-carbenium ion.
机译:N-甲苯磺酰基3,3-二烷基-2-(叔丁基二苯基甲硅烷基甲基)氮杂环丁烷在CH_2Cl _2中暴露于BF_3·OEt_2后,平稳地重排为相应的2-烯基-3-(叔丁基二苯基甲硅烷基)胺。该反应涉及顺序的〜σC-N键裂解,N-甲苯磺酰基-氨基甲基基团的1,2-迁移和所得叔碳鎓离子的去质子化。例如,由于N-甲苯磺酰基-氨基甲基的迁移而形成的碳正离子由于是叔或苄基而高度稳定,因此迁移与σ_(CN)键裂解同步进行,这导致对产物中带有叔丁基二苯基甲硅烷基甲基的碳原子的高度构型控制。与N-甲苯磺酰基取代的3-烷基-2-(叔丁基二苯基甲硅烷基甲基)氮杂环丁烷相反,相应的3,3-二烷基衍生物暴露于N-甲苯磺酰基-2-烯基-3-(叔丁基二苯基甲硅烷基)胺BF_3·OEt_2。该反应涉及顺序的σ_(C-N)键裂解,N-甲苯磺酰基-氨基甲基基团的1,2-迁移和所得叔碳鎓离子的去质子化。

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