Collect. Czech. Chem. Commun. 1980, 45, 559-583

Participation of 19-substituents in electrophilic additions to 6,7-unsaturated 5α-cholestane and B-homo 5α-cholestane derivatives; A case of competition between the participation of an ambident neighboring group and external nucleophile attack

Pavel Kočovský, Ladislav Kohout and Václav Černý

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


Hypobromous acid action upon the 6,7-unsaturated 19-substituted 5α-cholestans Va-Vc results in the formation of two types of products, the cyclic ethers IX as products of 5(O)n participation of the 19-substituent, and the bromohydrins X. All these compounds are formed from the 6α,7α-bromonium ions Va'-Vc'. Under the same conditions the B-homo-5α-cholestane derivatives VIIa-VIIc afforded solely the cyclic ethers XIV as products of 5(O)n participation of the 19-substituent in the cleavage of the bromonium ions VIIa'-VIIc'. Acid cleavage of the 6α,7α-epoxides VIb and VIc with aqueous perchloric acid or hydrobromic acid gave two types of products, i.e. the cyclic ethers XI and the diols XII or bromohydrines XIII. The cyclic ethers XI arise by 5(O)n participation of the 19-substituent. The B-homo-6α, 7α-epoxide VIIIc on cleavage with aqueous perchloric acid have solely the cyclic ether XVc and by treatment with hydrobromic acid VIIIc afforded the mixture of XVc, as the main product, and of the bromohydrin XVIc. Discussed is the similarity of the bromonium ion cleavage with the fission of the corresponding epoxides, the mechanism of these reactions and the difference in the behaviour of the isomeric olefins Ia-c, IIIa-c, Va-c and VIIa-c and epoxides IIb,c, IVb,c, VIb,c and VIIIb,c. The competition between ambident neighbouring group participation and external nucleophile attack is discussed as well as the dependence of the products ratio on the nucleophilicity of the attacking species.