Oligomeric flavanoids. Part 3. Structure and synthesis of phlobatannins related to (–)-fisetinidol-(4α,6)- and (4α,8)-(+)-catechin profisetinidins

Abstract

Several members of the novel class of natural ‘phlobaphene’ condensed tannins, representing the products of c-ring isomerization of 2,3-trans-3,4-trans-(–)-fisetinidol units present in (4,6)- and (4,8)-biflavanoid profisetinidins, have been characterized by ¹H n.m.r. n.o.e. difference spectroscopy. These include the functionalized 8,9-trans-9,1 0-cis-tetrahydropyrano[2,3-h]chromenes (9) and (12), and the [2,3-f]- and [2,3-g] regioisomers (14) and (19). Since the (4α,8)-biflavanoid (1) is subject to extensive base-catalysed rearrangement and epimerization, the protected 4-O-methyl ethers (E-ring)(2) and (6) were utilized to confirm the proposed structures of phlobatannins by stereospecific C-ring isomerization of (2) and (6) under basic conditions.