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Bis(imino)pyridine Cobalt-Catalyzed Dehydrogenative Silylation of Alkenes: Scope, Mechanism, and Origins of Selective Allylsilane Formation
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2014-08-12 , DOI: 10.1021/ja5060884 Crisita Carmen Hojilla Atienza 1 , Tianning Diao 1 , Keith J. Weller 2 , Susan A. Nye 2 , Kenrick M. Lewis 3 , Johannes G. P. Delis 4 , Julie L. Boyer 2 , Aroop K. Roy 2 , Paul J. Chirik 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2014-08-12 , DOI: 10.1021/ja5060884 Crisita Carmen Hojilla Atienza 1 , Tianning Diao 1 , Keith J. Weller 2 , Susan A. Nye 2 , Kenrick M. Lewis 3 , Johannes G. P. Delis 4 , Julie L. Boyer 2 , Aroop K. Roy 2 , Paul J. Chirik 1
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The aryl-substituted bis(imino)pyridine cobalt methyl complex, ((Mes)PDI)CoCH3 ((Mes)PDI = 2,6-(2,4,6-Me3C6H2-N═CMe)2C5H3N), promotes the catalytic dehydrogenative silylation of linear α-olefins to selectively form the corresponding allylsilanes with commercially relevant tertiary silanes such as (Me3SiO)2MeSiH and (EtO)3SiH. Dehydrogenative silylation of internal olefins such as cis- and trans-4-octene also exclusively produces the allylsilane with the silicon located at the terminus of the hydrocarbon chain, resulting in a highly selective base-metal-catalyzed method for the remote functionalization of C-H bonds with retention of unsaturation. The cobalt-catalyzed reactions also enable inexpensive α-olefins to serve as functional equivalents of the more valuable α, ω-dienes and offer a unique method for the cross-linking of silicone fluids with well-defined carbon spacers. Stoichiometric experiments and deuterium labeling studies support activation of the cobalt alkyl precursor to form a putative cobalt silyl, which undergoes 2,1-insertion of the alkene followed by selective β-hydrogen elimination from the carbon distal from the large tertiary silyl group and accounts for the observed selectivity for allylsilane formation.
中文翻译：
双（亚氨基）吡啶钴催化烯烃脱氢硅烷化：选择性烯丙基硅烷形成的范围、机制和起源
芳基取代的双（亚氨基）吡啶钴甲基配合物（（Mes）PDI）CoCH3（（Mes）PDI = 2,6-（2,4,6-Me3C6H2-N=CMe）2C5H3N）促进催化脱氢反应线性α-烯烃的甲硅烷基化以选择性地与商业相关的叔硅烷如 (Me3SiO)2MeSiH 和 (EtO)3SiH 形成相应的烯丙基硅烷。内烯烃（如顺式和反式 4-辛烯）的脱氢硅烷化也仅产生烯丙基硅烷，硅位于烃链的末端，从而形成一种高选择性贱金属催化的 CH 键远程官能化方法保留不饱和度。钴催化反应还使廉价的 α-烯烃能够作为更有价值的 α-烯烃的功能等价物，ω-二烯，并提供了一种独特的方法，用于将硅油与明确定义的碳间隔物进行交联。化学计量实验和氘标记研究支持活化钴烷基前体以形成推定的钴甲硅烷基，其经历烯烃的 2,1-插入，然后从大叔甲硅烷基团的远端碳选择性消除 β-氢，并解释观察到的烯丙基硅烷形成选择性。
更新日期：2014-08-12
中文翻译：
双（亚氨基）吡啶钴催化烯烃脱氢硅烷化：选择性烯丙基硅烷形成的范围、机制和起源
芳基取代的双（亚氨基）吡啶钴甲基配合物（（Mes）PDI）CoCH3（（Mes）PDI = 2,6-（2,4,6-Me3C6H2-N=CMe）2C5H3N）促进催化脱氢反应线性α-烯烃的甲硅烷基化以选择性地与商业相关的叔硅烷如 (Me3SiO)2MeSiH 和 (EtO)3SiH 形成相应的烯丙基硅烷。内烯烃（如顺式和反式 4-辛烯）的脱氢硅烷化也仅产生烯丙基硅烷，硅位于烃链的末端，从而形成一种高选择性贱金属催化的 CH 键远程官能化方法保留不饱和度。钴催化反应还使廉价的 α-烯烃能够作为更有价值的 α-烯烃的功能等价物，ω-二烯，并提供了一种独特的方法，用于将硅油与明确定义的碳间隔物进行交联。化学计量实验和氘标记研究支持活化钴烷基前体以形成推定的钴甲硅烷基，其经历烯烃的 2,1-插入，然后从大叔甲硅烷基团的远端碳选择性消除 β-氢，并解释观察到的烯丙基硅烷形成选择性。
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