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Cross-coupling reactions are usually associated with the metals of boron (Suzuki-Miyaura), zinc (Negishi), tin (Stille), and copper (Sonogashira) along with magnesium (Kumada).1 As a viable alternative to these metals the Hiyama-Denmark cross-coupling reactions involve organosilicon reagents as the nucleophilic partner in C-C bond forming cross-coupling protocols. The organosilanes have several advantages, including being readily prepared by a variety of approaches, excellent storage stability, ease of removal or recycling of the organosilane by-products, good functional group toleration, and low to non-toxicity profiles. The organosilane cross-coupling chemistry has been thoroughly reviewed.2 The use of sodium and potassium silanolates as the nucleophilic partner in the silicon-based cross-coupling transformations has been shown to be of practical utility.3

1. a. De Meijre, A.; Diederich, F. Eds. Metal-Catalyzed Cross-Coupling Reactions;Wiley-VCH: Weinheim, 2004. b. Bringmann, G.; Walter, R.; Weirich, R. Angew. Chem. Int. Ed. 1990, 29, 977. c. Negishi, E. “Handbook of Organopalladium Chemistry for Organic Synthesis” Wiley-Interscience: New York, 2002.
2. a. Hiyama, T. in “Metal-Catalyzed Cross-Coupling Reactions” Diederich, F.; Stang, P. J. Eds. Wiley-VCH: Weinheim, 1998; chapter 10. b. Denmark, S. E. Sweis, R. F. Acct. Chem. Res. 2002, 35, 835. c. Chang, W-T. T.; Smith, R. C.; Regens, C. S.; Bailey, A. D.; Werner, N. S.; Denmark, S. E. “Cross-Coupling with Organosilicon Compounds” Organic Reactions 2011, Vol. 75, pp d. Denmark, S. E. in “Silicon Compounds: Silanes and Silicones” Arkles, B. and Larson, G. L. Eds. Gelest, Inc. 2013, pp 63-70.
3. a. Denmark, S. E.; Baird, J. D. Chem. Eur. J. 2006, 8, 793. b. Denmark, S. E.; Smith, R. C.; Chang, W-T. T.; Muhuhi, J. M. J. Am. Chem. Soc.2009, 131, 3104. c. Denmark, S. E.; Smith, R. C.; Tymonko, S. A. Tetrahedron 2007, 63, 5730.
4. a. Smith, A. B. III; Hoye, A. T.; Martinez-Solorio, D.; Kim, W.-S.; Tong, R. J. Am. Chem. Soc.2012, 134, 4533. b. Nguyen, M. H.; Smith, A. B. III Org. Lett. 2014, 16, 2070.