The Transmetalation Process in Suzuki-Miyaura Reactions: Calculations Indicate Lower Barrier via Boronate Intermediate

被引：75
作者：
Ortuno, Manuel A. [1 ]
Lledos, Agusti [1 ]
Maseras, Feliu [1 ,2 ]
Ujaque, Gregori [1 ]
机构：
[1] Univ Autonoma Barcelona, Dept Quim, Cerdanyola Del Valles 08193, Spain
[2] Inst Chem Res Catalonia ICIQ, Tarragona 43007, Spain
来源：
CHEMCATCHEM | 2014年 / 6卷 / 11期
关键词：
boranes; cross-coupling; density functional calculations; palladium; transition states; CROSS-COUPLING REACTIONS; DENSITY-FUNCTIONAL THEORY; MOLECULAR-ORBITAL METHODS; OXIDATIVE ADDITION; ARYL HALIDES; BASIS-SETS; NONCOVALENT INTERACTIONS; PALLADIUM(0) COMPLEXES; REDUCTIVE ELIMINATION; TRANSITION-METALS;
D O I：
10.1002/cctc.201402326
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
Recent experimental reports have called into question the validity of the boronate mechanism (through a R-B(OH)(3)(-) intermediate) for the transmetalation step in the Suzuki-Miyaura cross-coupling, favoring instead the palladium hydroxo pathway (through an [LnPd(R')(OH)] intermediate). Herein we report DFT calculations with the M06 functional performed on realistic model systems, including a combination of explicit solvent molecules along with a continuum method. These computational results support the boronate mechanism. The mechanistic proposal is shown to be compatible with the available experimental evidence.
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收藏
页码：3132 / 3138
页数：7
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