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Synlett 2005(3): 529-531  
DOI: 10.1055/s-2005-862354
LETTER
© Georg Thieme Verlag Stuttgart · New York

4,4,6-Trimethyl-2-vinyl-1,3,2-dioxaborinane: An Efficient and Selective 2-Carbon Building Block for Vinylboronate Suzuki-Miyaura Coupling Reactions

Andrew P. Lightfoota, Steven J. R. Twiddleb, Andrew Whiting*b
a GlaxoSmithKline Pharmaceuticals, New Frontiers Science Park, Third Avenue, Harlow, Essex, CM19 5AW, UK
b Department of Chemistry, University of Durham, Science Laboratories, South Road, Durham, DH1 3LE, UK
Fax: +44(191)3843747; e-Mail: andy.whiting@durham.ac.uk;
Further Information

Publication History

Received 28 October 2004
Publication Date:
17 January 2005 (online)

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Abstract

An extremely simple and efficient palladium-catalyzed coupling procedure for the synthesis of functionalized styrenes and dienes is utilized to demonstrate how 4,4,6-trimethyl-2-vinyl-1,3,2-dioxaborinane can be employed to selectively undergo Suzuki-Miyaura coupling with a range of halide substrates.

Key words

Suzuki-Miyaura coupling - palladium(0) - vinylboronate ester - chemoselectivity

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Typical Procedure, Conditions A.
To an oven dried Schlenk-like tube under argon was added Pd(PPh3)4 (39 mg, 33.8 µmol) and t-BuOK (91 mg, 0.81 mmol), followed by THF (6 mL), substrate (0.675 mmol) and boronate 4 (0.125 g, 0.81 mmol). The tube was heated at 67 °C for 24 h before cooling, dilution with Et2O (30 mL) and filtration through Celite. This solution was treated with undecane (50 µL, 37.5 mg) and a portion was analyzed by GC. 1H NMR analysis to determine the Heck: Suzuki ratio, which was carried out after evaporation to give the crude product. Purification was carried out by silica gel column chromatography (hexane as eluant).