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Palladium-Catalyzed Suzuki–Miyaura Cross-Couplings with 2-Diethylphosphonato-Substituted Aryl- and Naphthylboronate Esters as the Nucleophilic Partner: A Complementary Approach to the Synthesis of Biaryl Monophosphonates

Lookup NU author(s): Dr Simon DohertyORCiD, Dr Julian Knight, Nicholas Ward, Daniel Perry, Dror Bittner, Professor Mike ProbertORCiD

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Abstract

This paper reports the first examples of Suzuki-Miyaura cross-couplings involving aryl- and naphthylphosphonate-based boronate esters as the nucleophilic partner. A systematic comparison of the performance of biaryl-like KITPHOS and XPHOS-based systems revealed that between them an electronically and sterically diverse range of substrates can be coupled with remarkable efficiency to afford high yields of the corresponding biaryl and heterobiaryl monophosphonates. The use of an aryl- and naphthylphosphonate-based boronate ester as the coupling partner presents an alternative and potentially complementary pathway to existing couplings in which the aryl- or naphthylphosphonate unit is typically introduced as the electrophile. The potential advantages associated with the use of this new class of coupling partner was clearly demonstrated by the palladium-catalyzed reaction between diethyl [2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]phosphonate and 1-bromo-2-methoxynaphthalene which gave the corresponding biaryl monophosphonate in 56% yield, a marked improvement on the 6% yield obtained from the reaction between 2-methoxy-1-naphthylboronic acid and diethyl (2-bromophenyl)phosphonate with the same catalyst under the same conditions. The potential utility of this new coupling combination was demonstrated by reducing one of the products, 2-methoxy-1-(2ʹ-diethoxyphosphorylphenyl)naphthylene, to the corresponding primary phosphine, which was subsequently converted into a diastereoisomeric mixture of the R,R-hexane-2,5-diol-derived phospholane in reasonable yield

Publication metadata

Author(s): Doherty S, Knight JG, Ward NAB, Perry DO, Bittner DM, Probert MR, Westcott SA

Publication type: Article

Publication status: Published

Journal: Organometallics

Year: 2014

Volume: 33

Issue: 19

Pages: 5209-5219

Print publication date: 13/10/2014

Online publication date: 05/09/2014

Date deposited: 16/12/2014

ISSN (print): 0276-7333

ISSN (electronic): 1520-6041

Publisher: Wiley

URL: http://dx.doi.org/10.1021/om500520z

DOI: 10.1021/om500520z

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