Synthesis of fatty acyl derivatives of 24-epibrassinolide

A number of fatty acid (palmitic, myristic and lauric) esters (both 3 alpha- and 3 beta-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 2 alpha-benzyl ethers. alpha,beta-Inversion of C-3 hydroxyl group was achieved through a consecutive oxidation-reduction reactions or by a nucleophilic substitution of the 3 alpha-mesylates. Treatment of the 3 alpha- and 3 beta-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'. (C) 2013 Elsevier Ltd. All rights reserved.