Synthesis of Linear Allylsilanes via Molybdenum-Catalyzed Regioselective Hydrosilylation of Allenes
Synthesis of Linear Allylsilanes via Molybdenum-Catalyzed Regioselective Hydrosilylation of Allenes
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DOI：
10.1021/acscatal.6b00627
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发表时间：
2016-05-01
期刊：
影响因子：
12.9
通讯作者：
Takai, Kazuhiko
中科院分区：
文献类型：
--
作者：
Asako, Sobi;Ishikawa, Sae;Takai, Kazuhiko
开发了一种简单的铼基催化体系用于联烯硅氢加成反应。单取代和二取代联烯与仲硅烷和叔硅烷的反应平稳地进行，并选择性地得到线性烯丙基硅烷。通过密度泛函理论研究来研究前所未有的线性选择性的起源，以揭示该反应由以下步骤组成：（1）从Mo（CO）（4）/丙二烯/硅烷加合物进行协同加氢氢化/Si-H氧化加成，以形成（π-烯丙基）钼，（2）烯丙基旋转从最初形成的（3）在受阻较少的烯丙基碳上还原消除，得到直链烯丙基硅烷。
A simple molybdenum-based catalytic system for hydrosilylation of allenes has been developed. The reactions of mono- and disubstituted allenes with secondary and tertiary silanes proceeded smoothly and selectively to afford linear allylsilanes. The origin of the unprecedented linear selectivity was investigated by density functional theory studies to reveal that the reaction consists of the following steps: (1) concerted hydromolybdation/Si-H oxidative addition from a Mo(CO)(4)/allene/silane adduct to form (pi-allyl)molybdenum, (2) allyl rotation from the initially formed (pi-allyl)molybdenum to a thermodynamically more stable isomer, and (3) reductive elimination at the less-hindered allyl carbon to afford a linear allylsilane.