Trimethylsilyl chloride TMSC

When the enone 182 was heated with trimethylsilyl chloride (TMSC) and sodium iodide in acetonitrile, a mixture of the 3,1-benzoxazines 183 and 184 in a ratio of 1 5 was formed stereospecifically. The a,/3-unsaturated ketones in TMSC/Nal first gave jS-iodoketones thereafter a tertiary carbo-cation was formed, and subsequent acetonitrile addition resulted in the oxazines 183 and 184 (89TL4741). 

A successful trapping reaction of a cyclopropyl ester enolate with trimethylsilyl chloride (TMSC) was first performed by Ainsworth and coworkers . In the reaction of 232 with lithium diisopropyl amide at — 78°C, followed by addition of TMSC, the ketene acetal 233 was formed in 10% yield as well as the silylated cyclopropane 234 (40%). Ketene acetals other than 233 are formed in yields > 90 %. 

Alkylation of the Uthium salt of TMSCHN2 (TMSC(Li)N2) gives a -trimethylsLlyl diazoalkanes which are useful for the preparation of vinylsilanes and acylsilanes. Decomposition of a-tri-methylsilyl diazoalkanes in the presence of a catalytic amount of Copper(I) Chloride gives mainly ( )-vinylsilanes (eq 12), while replacement of CuCl with rhodium(II) pivalate affords (Z)-vinylsilanes as the major products (eq 12). Oxidation of a-trimethylsilyl diazoalkanes with m-Chloroperbenzoic Acid in a two-phase system of benzene and phosphate buffer (pH 7.6) affords acylsilanes (a-keto silanes) (eq 12). ... 

Alkylation of the lithium salt of TMSCHN2 (TMSC(Li)N2) gives a-trimethylsilyl diazoalkanes which are useful for the preparation of vinylsilanes and acylsilanes. Decomposition of a-trimethylsilyl diazoalkanes in the presence of a catalytic amount of Copper(I) Chloride gives mainly ( )-vinylsilanes (eq 12), ... 

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See also in sourсe #XX -- [ ]

See also in sourсe #XX -- [ ]

See also in sourсe #XX -- [ , ]

See also in sourсe #XX -- [ ]

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