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. Lightfoot; Steven J. R. Twiddle; Andrew Whiting

doi:10.1055/s-2005-862354

LETTER

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. Lightfoot^a, Steven J. R. Twiddle^b, 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;

Abstract

All articles of this category

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

Full Text

References

1 Thirsk C. Whiting A. J. Chem. Soc., Perkin Trans. 1 2002, 8: 999

2a Omura S. Tanaka Y. Kanaya I. Shinose M. Takahashi Y. J. Antibiot. 1990, 43: 1034

2b Henaff N. Whiting A. Org. Lett. 1999, 1: 1137

2c Henaff N. Whiting A. Tetrahedron 2000, 56: 5193

3a Hunt AR. Stewart SK. Whiting A. Tetrahedron Lett. 1993, 34: 3599

3b Stewart SK. Whiting A. J. Organomet. Chem. 1994, 482: 293

3c Stewart SK. Whiting A. Tetrahedron Lett. 1995, 36: 3925

4a Nakagawa M. Furihata K. Hayakawa Y. Seto H. Tetrahedron Lett. 1991, 32: 659

4b Hasegawa T. Kamiya T. Henmi T. Iwasaki H. Yamatodani S. J. Antibiot. 1975, 28: 167

4c Nakagawa M. Toda Y. Furihata K. Hayakawa Y. Seto H. J. Antibiot. 1992, 45: 1133

5 Lightfoot AP. Maw G. Thirsk C. Twiddle SJR. Whiting A. Tetrahedron Lett. 2003, 44: 7645

6a Lando VR. Monteiro AL. Org. Lett. 2003, 5: 2891

6b Molander GA. Rivero MR. Org. Lett. 2002, 4: 107

6c Molander GA. Bernardi CR. J. Org. Chem. 2002, 67: 8424

7

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).

8 Uenishi J. Beau J. Armstrong RW. Kishi Y. J. Am. Chem. Soc. 1987, 109: 4756

Characterization data for products 8a-e, 8h and 10 was consistent with commercial samples. See:

9a 8f: Lebel HV. Paquet V. Organometallics 2004, 23: 1187

9b 8g: Chinkov N. Majumdar S. Marek I. J. Am. Chem. Soc. 2002, 124: 10282

10 Tinnemans AHA. Laarhoven WH. J. Chem. Soc., Perkin Trans. 2 1976, 10: 1104

11 Miyaura N. J. Organomet. Chem. 2002, 653: 54