Organosilicon compounds cross-coupling reactions

Hiyama, T. Organosilicon Compounds in Cross-Coupling Reactions. In Metal Catalyzed Cross-Coupling Reactions, Diederich, F., Stang, P. J., Eds. Wiley-VCH Weinhein, 1998 Chapter 10. 

Denmark, S. E. Sweis, R. F. Organosilicon Compounds in Cross-Coupling Reactions In Metal-Catalyzed C-C and C-N Cross-Coupling Reactions F. Diederich, A. deMei-jere, Eds. Wiley-VCH, 2004 Vol. 1 Chapt. 4. 

Hiyama T (1998) Organosilicon compounds in cross-coupling reactions. In de Mei-jere A, Diederich F (eds) Metal-catalyzed cross-coupling reactions. Wiley, Weinheim, p 421... 

The palladium-catalyzed cross-coupling reaction of organosilicon compounds is applied to the synthesis of biologically active compounds. Some examples are described in the following schemes artificial HMG-CoA reductase inhibitor, NK-104 (Scheme 7) [46-48], a precursor of a DNA topoisomerase inhibitor (Scheme 8) [49] and nucleosides (Eq. 40) [501. 

As discussed above, the cross-coupling reaction of organosilicon compounds proceeds stereospecifically, depending on the reaction conditions. Thus, the transformation C—Si C —C is demonstrated to be accompanied by chirality transfer. Now, the question arises of how to prepare organosilicon compounds whose chiral allylic carbon is substituted by a silyl group. The most accessible solution is asymmetric hydrosilylation of olefins [35]. We studied asymmetric hydrosilylation of 1-substituted 1,3-butadienes using... 

Because a C-Si bond is much less polarized than the C-metal bonds of the above organometallic reagents, the cross-coupling reaction using organosilicon compounds was not studied until 1988. 

We have found that alkynylsilanes are smoothly converted into alkynylcopper compounds by treatment with CuCl in l,3-dimethyl-2-imidazohdinone (DMI) the copper reagents can be isolated in good yields [563]. This study was the first example of preparation and isolation of organocopper compounds by use of organosilicon reagents. The Si-Cu transmetalation is applicable to the synthesis of alkynyl ketones by Cu-catalyzed alkynylation of acid chlorides (Scheme 10.217). We have also shown that a Cu-mediated system is effective in the cross-coupling reaction between arylsilanes or heteroarylsilanes and aryl hahdes [564]. 

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