Synthetic research of hepoxilins. 2. Hepoxilins A3: synthesis, configuration and composition of the hydrolysis products – trioxilins A3
P. M. Demin, L.L. Vasil'eva, G. I. Myagkova, K. K. Pivnitsky
M. V. Lomonosov Institute of Fine Chemical Technology, Moscow, Institute of Experimental Endocrinology, All-Union Endocrinology Research Centre, Academy of Medical Sciences of the USSR, Moscow
Abstract: A synthesis of C8-epimeric hepoxilins (HX) A3 esters was carried out by the allylic rearrangement of C10-epimeric HXB3 esters in the course of their mesylates hydrolysis. (8R)- and (8S)-configuration are assigned to the more and less polar epimers of HXA3 methyl esters, respectively, on the basis of the independently confirmed syn-stereoselecti-vity of the allylic mesylatesolvolysis. The composition of the HXA3 oxirane cycle hydrolysis products, trioxilins (TrX) A3, was investigated. The formation of two sets of regio-isomers, viz., (8,9,12)- and (8,11l,12)-TrXA3, was demonstrated, each one being a mixture of four compounds stereoisomeric at C8 and C9/C11. Structures and configurations at C8 of the individual TrXA3 are identified.
Russian Journal of Bioorganic Chemistry 1991, 17 (8):1133-1140