The Journal of Steroid Biochemistry and Molecular Biology 2013-09-01

Synthesis of fatty acyl derivatives of 24-epibrassinolide.

Vladimir A Khripach, Vladimir N Zhabinskii, Dmitrii V Tsavlovskii

Index: J. Steroid Biochem. Mol. Biol. 137 , 345-54, (2013)

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Abstract

A number of fatty acid (palmitic, myristic and lauric) esters (both 3α- and 3β-isomers) of epibrassinolide has been prepared as reference compounds for metabolic studies. Selective protection of the three of four hydroxyl groups of epibrassinolide was successively performed first as cyclic 22,23-methylboronates and then as 2α-benzyl ethers. α,β-Inversion of C-3 hydroxyl group was achieved through a consecutive oxidation-reduction reactions or by a nucleophilic substitution of the 3α-mesylates. Treatment of the 3α- and 3β-alcohols with palmitic, myristinic or lauric acid chlorides gave the corresponding esters. The hydrolysis of 22,23-methylboronates was performed after their transformation into 2-hydroxy-1,3,2-dioxaborolanes using a cation exchange column with DOWEX 50WX8 in NH4(+) form. Hydrogenolysis of the benzyl ethers catalyzed by palladium yielded the target compounds. This article is part of a Special Issue entitled "Synthesis and biological testing of steroid derivatives as inhibitors". Copyright © 2013 Elsevier Ltd. All rights reserved.