Mechanism of hypobromous acid addition to unsaturated steroids. Competition between neighboring group participation and external nucleophile attack

1982 ◽  
Vol 47 (1) ◽  
pp. 117-123 ◽  
Author(s):  
Pavel Kočovský ◽  
František Tureček ◽  
Václav Černý

Mechnism of hydrobromous acid addition to 2,3- and 5,6-unsaturated steroids bearing a 19-acetoxy group were established by means of isotopic labeling. In the cleavage of 2α,3α-bromonium ion III participation by the 19-acetoxyl predominates over external attack, 5(O)n process being the major (88%) and 7(O)π,n process the minor (10%) reaction. The external attack by water contributes only 2%. The 5α,6α-bromonium ion XI is cleaved by participation of the 19-acetoxyl at C(5) in a 6(O)π,n process (78%) via XII - XIII. Cleveage at C(6) leads to XIV and occurs partially with 7(O)π,n participation by the 19-acetoxyl (4%) and partially by external attack of water (8%). These results bring evidence for the formation of a seven-membered acetoxonium ion ring as intermediate in participation processes involving ester carbonyl groups.

1982 ◽  
Vol 47 (11) ◽  
pp. 3062-3076 ◽  
Author(s):  
Václav Černý ◽  
Pavel Kočovský

Reactions of the title compounds (bearing an OH, OCH3 or OCOCH3 group at C(19)) involve 5(O)n, 7(O)π,n-participation by the 19-substituent or attack by an external nucleophile. The 6(O)π,n-participation does not occur. The behavior of 1,2-unsaturated (or epoxidated) compounds has been compared with the earlier described 2,3-unsaturated or epoxidated analogs. The 1,2-type is genarally less prone to participation. The reasons for this behavior are discussed.


1980 ◽  
Vol 45 (11) ◽  
pp. 3199-3209 ◽  
Author(s):  
Pavel Kočovský ◽  
Václav Černý

Participation of the 19-methoxy and 19-acetoxy group in 3α,4α- and 4α,5α-epoxides IIIc, IVb,c on treatment with aqueous perchloric or hydrobromic acid is investigated and compared with acid treatment of structurally similar 19-substituted 6α,7α- and 5α,6α-epoxides V and VI and with the behavior of analogous 3α,4α- and 4α,5α-bromonium ions. The 3α,4α-epoxides III react readily with 5(O)n participation. The reaction is practically quantitative on perchloric acid treatment. Under the same conditions, the 19-methoxy-4α,5α-epoxide IVb suffers mainly external attack leading to the diol XIb. The neighboring group participation is solely a 5(O)n process giving rise to the cyclic ether X. The 19-acetoxy-4α,5α-epoxide IVc reacts predominantly with participation of the ambident acetoxy group. This reaction is exclusively a 6(O)π,n process affording the diol XVI. External attack proceeds to a limited extent to give the isomeric diol XIc. In this respect the latter compounds react quite analogously to 5α,6α-epoxides VI and 4α,5α- and 5α,6α-bromonium ions bearing 19-acetoxyl.


1983 ◽  
Vol 48 (12) ◽  
pp. 3618-3628 ◽  
Author(s):  
Pavel Kočovský

On reaction with hypobromous acid, the unsaturated alcohol IIIa yields the diequatorial bromo epoxide XIX arising from the 5α,6α-bromonium ion XVIIIa on cleavage at C(5) by 19b-hydroxyl group with 6(O)n participation. By contrast, the bromonium ion XVIIIb generated from the unsaturated methyl ether IIIb is cleaved by water as external nucleophile to yield the unstable diaxial bromohydrin XX which undergoes cyclization to the oxirane derivative XXI. A comparison with the reaction course in homologs of the type I and II permits the conclusion that the change in regioselectivity, generally possible outcome of the 5(O)n participation, is only possible for the 6(O)n process if the participating group is a hydroxyl.


1981 ◽  
Vol 46 (11) ◽  
pp. 2877-2891 ◽  
Author(s):  
Pavel Kočovský ◽  
František Tureček

Hypobromous acid addition to the diene VII yields two epimeric dibromo 6β,19a-epoxides, XVI (main product) and XVII, via the intermediary bromohydrin XIII. Products due to C-C bond formation were not observed. This fact is attributed to the mutual perpendicular arrangement of π-orbitals of the two double bonds in the diene VII. Hypobromous acid action upon the 5α,6β-diol IX and the dimethoxy derivative X afforded analogous products of 6(O)n participation by the 6β-substituent, i.e. the cyclic ethers XXII, XXIII and XXIV, XXV. Under the same conditions the 6β-acetoxy derivative XI gave a mixture of the cyclic ethers XXII and XXIII as products of 6(O)n participation, and the rearranged ketone XXVI. Mechanism of this rearrangement is discussed.


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