Integrated reactions using addition to conjugated imines and iminium salts
Integrated reactions using addition to conjugated imines and iminium salts
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DOI：
10.1351/pac-con-12-01-03
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发表时间：
2012-06
影响因子：
1.8
通讯作者：
Takafumi Nishi;Isao Mizota;M. Shimizu
中科院分区：
文献类型：
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作者：
Takafumi Nishi;Isao Mizota;M. Shimizu
近年来，在合成生物活性材料和功能材料的许多关键步骤中，都利用了对亚氨基的亲核加成反应。本文综述了α-亚胺酯的综合“umpolung”反应和用亚胺盐作为反应性亲电试剂的研究进展。对于混合反应，讨论了以下五种反应：(1)n -烷基化/均偶联；(2) n -乙基化/ c -烯丙基化串联；(3) n -乙基化/ c -氰化串联；(4)用三（三甲基硅基）铝还原亚胺；(5) n -烷基化和Claisen重排。此外，还讨论了烷氧羰基亚胺的生成和反应。它们很容易由三取代的氨基烯基硅基缩醛通过氧化制备，随后各种亲核试剂的亲核加成容易提供加成产物。
Recently, nucleophilic addition reactions to imino functions have been utilized in many crucial steps for the synthesis of bioactive and functional materials. This article summarizes the integrated “umpolung” reactions of α-imino esters and the use of iminium salts as reactive electrophiles. Regarding the umpolung reactions, the following five reactions are discussed: (1) N-alkylation/homocoupling; (2) tandem N-ethylation/C-allylation; (3) tandem N-ethylation/C-cyanation; (4) reduction of imines with tris(trimethylsilyl)aluminum; and (5) N-alkylation and Claisen rearrangement. Moreover, the generation and reactions of alkoxycarbonyl iminium species are also discussed. These are prepared easily from trisubstituted amino ketene silyl acetals by oxidation, and the subsequent nucleophilic addition of various nucleophiles readily affords the addition products.