一种形成碳-碳键的新方法：有氧钯催化有机金属试剂与苯乙烯的还原偶联反应的发展。
A new approach to carbon-carbon bond formation: Development of aerobic Pd-catalyzed reductive coupling reactions of organometallic reagents and styrenes.
作者信息
Gligorich Keith M, Iwai Yasumasa, Cummings Sarah A, Sigman Matthew S
机构信息
Department of Chemistry, University of Utah, 315 South 1400 East Salt Lake City, UT 84112, USA.
出版信息
Tetrahedron. 2009 Jun 27;65(26):5074-5083. doi: 10.1016/j.tet.2009.03.096.
Abstract
Alkenes are attractive starting materials for organic synthesis and the development of new selective functionalization reactions are desired. Previously, our laboratory discovered a unique Pd-catalyzed hydroalkoxylation reaction of styrenes containing a phenol. Based upon deuterium labeling experiments, a mechanism involving an aerobic alcohol oxidation coupled to alkene functionalization was proposed. These results inspired the development of a new Pd-catalyzed reductive coupling reaction of alkenes and organometallic reagents that generates a new carbon-carbon bond. Optimization of the conditions for the coupling of both organostannanes and organoboronic esters is described and the initial scope of the transformation is presented. Additionally, several mechanistic experiments are outlined and support the rationale for the development of the reaction based upon coupling alcohol oxidation to alkene functionalization.
摘要
烯烃是有机合成中颇具吸引力的起始原料，人们期望开发新的选择性官能团化反应。此前，我们实验室发现了一种独特的钯催化含酚苯乙烯的氢烷氧基化反应。基于氘标记实验，提出了一种涉及需氧醇氧化与烯烃官能团化偶联的机理。这些结果启发了一种新的钯催化烯烃与有机金属试剂的还原偶联反应的开发，该反应可生成新的碳 - 碳键。描述了有机锡烷和有机硼酸酯偶联条件的优化，并展示了该转化反应的初步适用范围。此外，概述了几个机理实验，这些实验支持了基于醇氧化与烯烃官能团化偶联来开发该反应的理论依据。
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