Mechanism of Cu-catalyzed aryl boronic acid halodeboronation using electrophilic halogen: development of a base-catalyzed iododeboronation for radiolabeling applications

Molloy, J. J., O'Rourke, K., Frias, C. P., Sloan, N., West, M. J., Pimlott, S. L. , Sutherland, A. and Watson, A. J.B. (2019) Mechanism of Cu-catalyzed aryl boronic acid halodeboronation using electrophilic halogen: development of a base-catalyzed iododeboronation for radiolabeling applications. Organic Letters, 21(7), pp. 2488-2492. (doi: 10.1021/acs.orglett.9b00942) (PMID:30908055)

Abstract

An investigation into the mechanism of Cu-catalyzed aryl boronic acid halodeboronation using electrophilic halogen reagents is reported. Evidence is provided to show that this takes place via a boronate-driven ipso-substitution pathway and that Cu is not required for these processes to operate: general Lewis base catalysis is operational. This in turn allows the rational development of a general, simple, and effective base-catalyzed halodeboronation that is amenable to the preparation of 125I-labeled products for SPECT applications.

• Item Type: Articles
• Additional Information: Also funded by CAPES/Science Without Borders (CAPES/SwB Proc. no. BEX5935/13-0).
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Pimlott, Dr Sally and Watson, Dr Allan and O'Rourke, Kerry and Sloan, Dr Nikki and Sutherland, Professor Andrew
• Authors: Molloy, J. J., O'Rourke, K., Frias, C. P., Sloan, N., West, M. J., Pimlott, S. L., Sutherland, A., and Watson, A. J.B.
• College/School: College of Medical Veterinary and Life Sciences > School of Medicine, Dentistry & Nursing; College of Science and Engineering > School of Chemistry
• Journal Name: Organic Letters
• Publisher: American Chemical Society
• ISSN: 1523-7060
• ISSN (Online): 1523-7052
• Published Online: 25 March 2019
• Copyright Holders: Copyright © 2019 American Chemical Society
• First Published: First published in Organic Letters 21(7):2488-2492
• Publisher Policy: Reproduced under a Creative Commons License

Project Code	Award No	Project Name	Principal Investigator	Funder's Name	Funder Ref	Lead Dept
304896	0	EPSRC-IAA: Early Stage Commercialisation of a PET Imaging Agent for the Detection of Cardiovascular Disease and Cancer	Andrew Sutherland	Engineering and Physical Sciences Research Council (EPSRC)	EP/R511705/1	Chemistry
60895	1	Engineering and Physical Sciences Doctoral Training Grant 2012-16	Mary Beth Kneafsey	Engineering and Physical Sciences Research Council (EPSRC)	EP/K503058/1	VPO VICE PRINCIPAL RESEARCH & ENTERPRISE