The synthesis and the rearrangement of O-silyl-O-alkyl keteneacetals into esters of silylacetic acid

Lutsenko, I. F.; Baukov, Yu. I.; Burlachenko, G. S.; Khasapov, B. N.

doi:10.1016/s0022-328x(00)82246-9

Cited by 43 publications

(2 citation statements)

References 13 publications

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“…It is possible to prepare , -disubstituted -silyl esters via alkylation of the -silyl esters (vida infra). 19 This was used to prepare ethyl 2-methyl-2-(methyldiphenylsilyl)propionate in 75% yield (eq 9). This compound can be R2 Rl?HC0*Et ^ £---R1-CC02E.…”

Section: Methyldiphenylsilylation Of Monosubstitutedmentioning

confidence: 99%

The chemistry of .alpha.-silyl carbonyl compounds. 17. Methyldiphenylsilylation of ester and lactone enolates

Larson¹,

Maldonado²,

Fuentes³

et al. 1988

J. Org. Chem.

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The reactions of a variety of ester and lactone enolates with methyldiphenylchlorosilane were studied. The Cversus O-silylation, leading to the -silyl ester or lactone and silyl ketene acetal, respectively, was studied as a function of the structure of the ester or lactone and the reaction conditions. It was found that all simple acetates are C-silylated irrespective of the steric demands of the alcohol portion of the ester. Esters that are monosubstituted in the -position are cleanly C-silylated with the notable exceptions of ethyl phenylacetate and ethyl phenoxyacetate, both of which give mixtures of C-and O-silylation. The , -disubstituted esters give only O-silylation, but the a,«-substituted -silyl esters are readily prepared by the alkylation of the appropriate monosubstituted -silylated ester. The reaction of the lithium enolate of ethyl acetate and ierf-butyl acetate with (S)-(-)-l-naphthylphenylmethylchlorosilane showed the reaction to occur with inversion of configuration at silicon. Methylation of fert-butyl (1 -naphthylphenylmethylsilyl)acetate gave a 91:9 mixture of diastereomeric -silyl propionates, which could not be separated. It was found that only the y-lactones gave C-silylation with -valerolactone and e-caprolactone giving O-silylation.The silylation of ester or lactone enolates can occur to produce the silyl ketene acetals or the -silyl esters or lactones, all synthetically useful classes of compounds, as a result of silylation at the Oor C-terminus of the enolate

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Section: Methyldiphenylsilylation Of Monosubstitutedmentioning

confidence: 99%

The chemistry of .alpha.-silyl carbonyl compounds. 17. Methyldiphenylsilylation of ester and lactone enolates

Larson¹,

Maldonado²,

Fuentes³

et al. 1988

J. Org. Chem.

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“…When a toluene solution of 14 is photolyzed at -76°C, a photostationary state consisting of 14 and its Z isomer, 15, is reached in one hour (14/15 = 56:44). Upon heating to 34°C, isomer 15 is converted quantitatively to a single isomer of 2-methyl-4-trimethysiloxy)-2, 4-pentadiene 16. The free energy of activation was estimated to be 23 kcal/mol.…”

Section: Mesimentioning

confidence: 99%