cis-Hydroxylation of a Synthetic Steroid Intermediate with Iodine, Silver Acetate and Wet Acetic Acid

Woodward, R. B.; Brutcher, Frederick V.

doi:10.1021/ja01534a053

Cited by 216 publications

(102 citation statements)

References 3 publications

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“…The crude product had an i.r. spectrum very similar to that of 5a-cholestan-3-one-2a-yl p-anisate (14). The product was purified by t.1.c.…”

Section: Oxidation Of the Steroid Hydroxyanisates Withmentioning

confidence: 79%

“…Woodward-Pre'vost Reaction The reaction of an olefin with iodine and silver acetate in wet acetic acid (14), often referred to as the Woodward-PrCvost reaction, is another process which is believed to proceed via a dioxolenium species, specifically an acetoxonium ion. If this is indeed the case, it would be expected that the hydroxy-acetate obtained as the direct product of the reaction, prior to the usual saponification to the glycol, would have the hydroxyl group equatorial and the acetoxyl function axial.…”

Section: Stereochemistry Of the Hydroxy-ester From Thementioning

confidence: 99%

“…spectrum. Crystallization from pentane gave 5a-cholestan-3-one2a-yl p-anisate (14); m.p. 148-150"; [aID f 1 0 5 " ; v,,, 1725, 1705 cm-'.…”

Section: Oxidation Of the Steroid Hydroxyanisates Withmentioning

confidence: 99%

“…as the faster moving component of the mixture from hydrolysis of 7. Structure 12 for this product follows from (a) the formation of the 2a,3a-diol (11) on saponification, and (6) production of 2a-anisoxy-5a-cholestan-3-one (14) on Jones' oxidation. The same material (14) was obtained by acid-catalyzed epimerization of 18.…”

Section: Introductionmentioning

confidence: 99%

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Remarkable stereoselectivity in the hydrolysis of dioxolenium ions and orthoesters fused to anchored six-membered rings

King¹,

Allbutt²

1970

Can. J. Chem.

109

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Hydrolysis of dioxolenium (acyloxonium) ions fused to anchored six-membered rings gives almost exclusively that hydroxyester in which the ester function is axial (and the hydroxyl group equatorial). With the exception of the orthoformate, a group of related orthoesters reacted similarly. The potential utility of these observations in stereoselective synthesis is suggested by the following examples. (a) With trans-decalin-cis-2,3-diol (21) formation of the mono-benzoate via the orthoester leads to the axial ester (23d) in good yield; this procedure is complementary to reaction with benzoyl chloride and pyridine, which gives the equatorial ester (24d) as the only isolated product. (b) The action of silver acetate and iodine in wet acetic acid (the Woodward-Prkvost reaction) on trans-A'-octalin gives the axial acetateequatorial alcohol (236) again as the only significant product. The generality of this stereoselectivity is further supported by a number of individual examples drawn from the chemistry of carbohydrates. A rationalization is offered which qualitatively accounts for the observed stereoselectivity and its absence in the hydrolysis of the orthoformate, and which is based on the differences in steric strain among the possible transition states that fulfil the stereoelectronic requirements of dialkoxycarbonium ion formation.

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“…The crude product had an i.r. spectrum very similar to that of 5a-cholestan-3-one-2a-yl p-anisate (14). The product was purified by t.1.c.…”

Section: Oxidation Of the Steroid Hydroxyanisates Withmentioning

confidence: 79%

Section: Stereochemistry Of the Hydroxy-ester From Thementioning

confidence: 99%

“…spectrum. Crystallization from pentane gave 5a-cholestan-3-one2a-yl p-anisate (14); m.p. 148-150"; [aID f 1 0 5 " ; v,,, 1725, 1705 cm-'.…”

Section: Oxidation Of the Steroid Hydroxyanisates Withmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Remarkable stereoselectivity in the hydrolysis of dioxolenium ions and orthoesters fused to anchored six-membered rings

King¹,

Allbutt²

1970

Can. J. Chem.

109

View full text Add to dashboard Cite

show abstract

“…Our speculation has no dissonance with that of the mechanism for the nucleophilic addition of alkyl Grignard reagents to a 22-formyl group17, [28][29][30] and also "with that of the mechanism for halohydrinations and haloacyloxylations 18 ) of a 22-0Iefin.…”

mentioning

confidence: 66%