{uni_hamburg} Short: III/35D2

{ALF}

{ALF} Silylating agent (see Appendix 4): J. Chromat., 147, 291 (1978). Dimethylphenylsilyl (DMPS) ethers are somewhat more resistant to hydrolysis than TMS and are useful in the chromatographic analysis of monosaccharides with UV detection: J. Chromat., 264, 99 (1983); Carbohydr. Res., 119, 241 (1983). See also Dimethyl­phenyl­silane, L04558. The lithio-derivatives of esters and lactones are silylated by DMPSCl on carbon (TMSCl gives O-silylation): J. Am. Chem. Soc., 103, 2418 (1981).

{ALF} See also: J. Chem. Soc., Perkin 1, 1209 (1998).

{ALF} The reactions of various metallated DMPS derivatives have been extensively studied by Fleming's group and others. DMPSLi gives an organocopper species with CuI which undergoes conjugate addition to enones, to give ß-silyl ketones: J. Chem. Soc., Perkin 1., 2520 (1981):

{ALF} For a study of diastereoselectivity in the preparation of ß-silyl esters from ɑß-unsaturated esters and amides attached to chiral auxiliaries, see: J. Chem. Soc., Perkin 1, 303 (1995). For a brief feature on Phenyldimethylsilyllithium, see: Synlett, 1522 (2000).

{ALF} Aryl-, alkenyl- and alkynyldimethylchlorosilanes undergo homo-coupling in the presence of TBAF and a catalytic amount of CuI to give biaryls or the corresponding symmetrical dienes or diynes in high yield: J. Chem. Soc., Perkin 1, 797 (1997).

{uni_hamburg} Short: III/35F

{ALF} The DMPS group attached to carbon may function as a masked OH group. Protodesilylation gives the silyl fluoride, which can be converted to the alcohol with overall retention of configuration by reaction with m-CPBA, peracetic acid/ Br2, or peracetic acid/ Mg(OAc)2 with or without Pd(II) catalysis. For a detailed study, see: J. Chem. Soc., Perkin 1, 317 (1995):