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The Transmetalation Process in Suzuki–Miyaura Reactions: Calculations Indicate Lower Barrier via Boronate Intermediate
Author(s) -
Ortuño Manuel A.,
Lledós Agustí,
Maseras Feliu,
Ujaque Gregori
Publication year - 2014
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201402326
Subject(s) - transmetalation , chemistry , palladium , computational chemistry , solvent , molecule , combinatorial chemistry , organic chemistry , catalysis
Recent experimental reports have called into question the validity of the boronate mechanism (through a RB(OH) 3 − intermediate) for the transmetalation step in the Suzuki–Miyaura cross‐coupling, favoring instead the palladium hydroxo pathway (through an [L n Pd(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.