钯催化烯丙基硅醇盐与芳基溴化物交叉偶联反应的立体化学过程
On the stereochemical course of palladium-catalyzed cross-coupling of allylic silanolate salts with aromatic bromides.
作者信息
Denmark Scott E, Werner Nathan S
机构信息
Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, USA.
出版信息
J Am Chem Soc. 2010 Mar 17;132(10):3612-20. doi: 10.1021/ja910804u.
Abstract
The stereochemical course of palladium-catalyzed cross-coupling reactions of an enantioenriched, alpha-substituted, allylic silanolate salt with aromatic bromides has been investigated. The allylic silanolate salt was prepared in high geometrical (Z/E, 94:6) and high enantiomeric (94:6 er) purity by a copper-catalyzed S(N)2' reaction of a resolved allylic carbamate. Eight different aromatic bromides underwent cross-coupling with excellent constitutional site-selectivity and excellent stereospecificity. Stereochemical correlation established that the transmetalation event proceeds through a syn S(E)' mechanism which is interpreted in terms of an intramolecular delivery of the arylpalladium electrophile through a key intermediate that contains a discrete Si-O-Pd linkage.
摘要
研究了对映体富集的α-取代烯丙基硅醇盐与芳基溴化物在钯催化下交叉偶联反应的立体化学过程。通过拆分的烯丙基氨基甲酸酯的铜催化S(N)2'反应，以高几何纯度（Z/E，94:6）和高对映体纯度（94:6 er）制备了烯丙基硅醇盐。八种不同的芳基溴化物发生交叉偶联反应，具有优异的结构位点选择性和立体专一性。立体化学关联表明，转金属化过程通过顺式S(E)'机制进行，这可以通过一个关键中间体进行分子内芳基钯亲电试剂传递来解释，该中间体包含一个离散的Si-O-Pd键。
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