• For facile O-silylation of tertiary alcohols in the presence of Mg metal, see: Synlett, 1025 (2000).
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For cleavage of ethers, see Sodium iodide, A15480.•
Conjugated enones give trimethylsilyloxydienes. For examples, see: Org. Synth. Coll., 6, 445 (1988); 7, 282 (1990). TMS chloride, LiBr and trimethylamine in THF is a convenient system for silylation of enones: Acta Chem. Scand., 43, 188 (1989). The same combination converts ɑ- and ?-diketones to their bis silyl enol ethers: Acta Chem. Scand., 43, 304 (1989). See also Trimethylsilyl trifluoromethanesulfonate, A12535.• Carbonyl compounds can be converted to their silyl enol ethers, e.g. with triethylamine in DMF: Org. Synth. Coll., 6, 327 (1988); 7,424 (1990); 8, 460 (1993); or using catalysis with NaI: Org. Synth. Coll., 9, 573 (1998).
• For further details and reviews, see Appendix 4.
• The conversion of alcohols to alkyl chlorides requires catalysis, e.g. SeO2: J. Org. Chem., 53, 3634 (1988), or by DMSO: J. Org. Chem., 60, 2638 (1995). The same system is also effective in opening epoxides.
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Silylation at carbon atoms is usually carried out using organometallic reagents, e.g. vinylmagnesium bromide: Org. Synth. Coll., 6, 1033 (1988). In aromatic rings, silyl groups can be introduced by directed metallation, followed by silylation; see e.g.: J. Org. Chem., 49, 4657 (1989). The silyl substituents can readily be replaced by electrophiles, allowing "abnormal" patterns of substitution. See 1,3-Dimethoxybenzene, A13380.
腐蚀性 (C)
易燃性 (F)
有害性 (Xn)
