4.4.9 Product Subclass 9: Silylzinc Reagents

Abstract

This chapter is a revision of the contribution on silylzinc reagents published in 2001, which describes the preparation and application of triorganosilylzinc compounds. Homo silylzinc reagents, such as bis(triphenylsilyl)zinc(II) [(Ph₃Si)₂Zn] and lithium tris[dimethyl(phenyl)silyl]zincate [(PhMe₂Si)₃ZnLi], as well as hetero or mixed silylzinc reagents, such as lithium [dimethyl(phenyl)silyl]dimethylzincate [(PhMe₂Si)ZnMe₂Li] and (biphenyl-2,2´-diolato)(tert-butyl)[dimethyl(phenyl)silyl]zincates {M₂Zn(t-Bu)[(2-OC₆H₄)₂](SiMe₂Ph); M = Li, MgCl}, are prepared with relative ease and are utilized in a variety of synthetic applications. These reagents react under a variety of conditions with unsaturated organic substrates to afford synthetically useful triorganosilylated species.

Key words

bis(triorganosilyl)zincs - dialkyl(triorganosilyl)zincates - dianionic silylzincates - catalysis - vinylsilanes - 3-(triorganosilyl) ketones - allylsilanes

• 1 Wiberg E, Stecher O, Andrascheck HJ, Kreuzbichler L, Staude E. Angew. Chem. Int. Ed. Engl. 1963; 2: 507

• 2 Rösch L, Altnau G. Angew. Chem. Int. Ed. Engl. 1979; 18: 60

• 3 Tückmantel W, Oshima K, Nozaki H. Chem. Ber. 1986; 119: 1581

• 4 Uchiyama M, Kondo Y. J. Synth. Org. Chem., Jpn. 2006; 64: 1180

• 5 Vaughan A, Singer RD. Tetrahedron Lett. 1995; 36: 5683

• 6 MacLean BL, Hennigar KA, Kells KW, Singer RD. Tetrahedron Lett. 1997; 38: 7313

• 7 Okuda Y, Wakamatsu K, Tückmantel W, Oshima K, Nozaki H. Tetrahedron Lett. 1985; 26: 4629

• 8 Crump RANC, Fleming I, Urch CJ. J. Chem. Soc., Perkin Trans. 1 1994; 701

• 9 Wakamatsu K, Nonaka T, Okuda Y, Tückmantel W, Oshima K, Utimoto K, Nozaki H. Tetrahedron 1986; 42: 4427

• 10 Fleming I, Lee D. J. Chem. Soc., Perkin Trans. 1 1998; 2701

• 11 Lipshutz BH, Sclafani JA, Takanami T. J. Am. Chem. Soc. 1998; 120: 4021

• 12 Uchiyama M, Koike M, Kameda M, Kondo Y, Sakamoto T. J. Am. Chem. Soc. 1996; 118: 8733

• 13 Nakamura S, Uchiyama M, Ohwada T. J. Am. Chem. Soc. 2004; 126: 11 146

• 14 Morizawa Y, Oda H, Oshima K, Nozaki H. Tetrahedron Lett. 1984; 25: 1163

• 15 Auer G, Weiner B, Oestreich M. Synthesis 2006; 2113

• 16 Weickgenannt A, Oestreich M. Chem.–Eur. J. 2010; 16: 402

• 17 Hayami H, Sato M, Kanemoto S, Morizawa Y, Oshima K, Nozaki H. J. Am. Chem. Soc. 1983; 105: 4491

• 18 Auer G, Oestreich M. Chem. Commun. (Cambridge) 2006; 311

• 19 Nakamura S, Uchiyama M, Ohwada T. J. Am. Chem. Soc. 2005; 127: 13 116

• 20 Nakamura S, Yonehara M, Uchiyama M. Chem.–Eur. J. 2008; 14: 1068

• 21 Oestreich M, Weiner B. Synlett 2004; 2139