The transmetalation process in Suzuki-Miyaura reactions: Calculations indicate lower barrier via boronate intermediate

Manuel A. Ortuño; Agustí Lledós; Feliu Maseras; Gregori Ujaque

doi:10.1002/cctc.201402326

The transmetalation process in Suzuki-Miyaura reactions: Calculations indicate lower barrier via boronate intermediate

Manuel A. Ortuño, Agustí Lledós, Feliu Maseras, Gregori Ujaque

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

64 Scopus citations

Abstract

Recent experimental reports have called into question the validity of the boronate mechanism (through a R-B(OH₃^- intermediate) for the transmetalation step in the Suzuki-Miyaura cross-coupling, favoring instead the palladium hydroxo pathway (through an [L_nPd(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.

Original language	English (US)
Pages (from-to)	3132-3138
Number of pages	7
Journal	ChemCatChem
Volume	6
Issue number	11
DOIs	https://doi.org/10.1002/cctc.201402326
State	Published - Nov 2014

Bibliographical note

Publisher Copyright:
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords

Boranes
Cross-coupling
Density functional calculations
Palladium
Transition states

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AU - Ujaque, Gregori

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The transmetalation process in Suzuki-Miyaura reactions: Calculations indicate lower barrier via boronate intermediate

Abstract

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