Selective Silylative Reduction of Pyridines Leading to Structurally Diverse Azacyclic Compounds with the Formation of sp3 C-Si Bonds
Selective Silylative Reduction of Pyridines Leading to Structurally Diverse Azacyclic Compounds with the Formation of sp3 C-Si Bonds
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DOI：
10.1021/jacs.5b09209
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发表时间：
2015-12-09
影响因子：
15
通讯作者：
Chang, Sukbok
中科院分区：
文献类型：
--
作者：
Gandhamsetty, Narasimhulu;Park, Sehoon;Chang, Sukbok
三（五氟苯基）硼烷催化吡啶的甲硅烷基化还原反应，选择性地在氮杂环产物的氮原子的β位形成sp（3）C-Si键。根据吡啶取代基的位置和性质，在硼烷催化下以高选择性获得结构多样的氮杂环。机理研究阐明了这种多重还原级联中的硅氢加成顺序：取决于取代基位置，作为初始步骤的1，2-或1，4-硅氢加成，随后是烯胺双键的选择性硅氢加成，最终得到β-甲硅烷基化的氮杂环化合物。
Tris(pentafluorophenyl)borane-catalyzed silylative reduction of pyridines has been developed giving rise to the formation of sp(3) C-Si bonds selectively beta to the nitrogen atom of azacyclic products. Depending on the position and nature of pyridine substituents, structurally diverse azacycles are obtained with high selectivity under the borane catalysis. Mechanistic studies elucidated the sequence of hydrosilylation in this multiple reduction cascade: 1,2- or 1,4-hydrosilylation as an initial step depending on the substituent position, followed by selective hydrosilylation of enamine double bonds eventually affording beta-silylated azacydic compounds.