Steroids and Walden inversion. Part LXIV. A reinvestigation of the deamination of 2-, 4-, and 7-amino-5a-cholestane
- 1 January 1968
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society C: Organic
- p. 2211-2215
- https://doi.org/10.1039/j39680002211
Abstract
Equatorial 2α-, 4α- and 7β-amino-5α-cholestane are deaminated in acetic or aqueous acetic acid with predominant but not exclusive retention accompanied by some elimination. Axial 4β- and 7α-amino-5α-cholestane are deaminated mainly with elimination, probably owing to the adjacent tertiary 5α- or 8β-hydrogen atom. 2β-Amino-5α-cholestane undergoes considerable elimination but also yields alcohols with predominant retention and acetates with predominant inversion. The ratio of epimeric alcohols formed differs considerably from the ratio of epimeric acetates produced in all these deaminations. The deamination process appears to be a complex reaction, greatly influenced by steric environment, which proceeds by a combination of SNi, SN2, and E2 mechanisms involving the diazonium ion, and by SN1 and E1 mechanisms involving the intermediate solvated carbonium ion.Keywords
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