Tandem Chemoselective Suzuki-Miyaura Cross-Coupling Enabled by Nucleophile Speciation Control

• Published in: Angewandte Chemie International Edition Vol. 54; no. 34; pp. 9976 - 9979
• Main Authors: Seath, Ciaran P., Fyfe, James W. B., Molloy, John J., Watson, Allan J. B.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 17-08-2015; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Benzene Derivatives - chemical synthesis; Benzene Derivatives - chemistry; Bonding; Boron; Boronic Acids - chemistry; Catalysis; Chemical reactions; chemoselectivity; Cross coupling; Formations; Molecular Structure; Nucleophiles; Organometallic Compounds - chemistry; palladium; Speciation; Strategy; cross-coupling; chemoselectivity; palladium; boron; speciation
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201504297

Control of boronic acid speciation is presented as a strategy to achieve nucleophile chemoselectivity in the Suzuki–Miyaura reaction. Combined with simultaneous control of oxidative addition and transmetalation, this enables chemoselective formation of two CC bonds in a single operation, providing a method for the rapid preparation of highly functionalized carbogenic frameworks.
Breaking the limit: Chemoselective Suzuki–Miyaura cross‐coupling has previously been limited to single CC bond formation due to a lack of nucleophile selectivity. Manipulation of boron speciation enables complete chemoselective control of the Suzuki–Miyaura reaction, allowing harmonized sequential cross‐coupling in a single operation.