Collect. Czech. Chem. Commun. 1983, 48, 3643-3659

Competition of two participating groups in hypobromous acid addition to some 4-cholestene derivatives

Pavel Kočovský

Institute of Organic Chemistry and Biochemistry, Czechoslovak Academy of Sciences, 166 10 Prague 6


Hypobromous acid addition to the 4,5-unsaturated hydroxy acetate VIII results in formation of the cyclic bromo ether XXIXa as a product of 5(O)n participation. Participation by hydroxy group is thus preferred over 5(O)π,n process by acetoxyl. Under the same conditions the 4,5-unsaturated diacetate IX afforded the diaxial bromohydrin XXXI arising from 4α,5α-bromonium ion with 5(O)π,n participation by the 3β-acetoxyl whereas an alternative 6(O)π,n participation by the 19-acetoxyl is not operative. The 3-epimeric diacetate XV reacts with hypobromous acid in a more complex way: the molecule is attacked by the electrophile from both α- and β-sites to give two diastereoisomeric bromonium ions XXXII and XXXIII. The former is simply cleaved with water as an external nucleophile to afford the diaxial bromohydrin XXXIV. The latter undergoes fission both with 5(O)π,n and 6(O)π,n participation: The first route leads to the trans-bromohydrin XXXVI. In the second pathway the acyloxonium ion XXXVII postulated as an intermediate is further cleaved with 6(O)π,n participation by 19-acetoxyl to give the acyloxonium ion XXXVIII, which is trapped by water to yield an unusual cis-bromohydrin XXXIX. The differences in the reaction course are discussed.