Abstract
Pairs of 8- and 6-functionalized (Br, OH, OAc, CO2Me, and CH2Me groups) 3′,4′,5,7-tetra-O-methyl-(+)-catechins available through selective bromination and debromination reactions and hence via lithio-analogues, provide diagnostic chemical shifts of their residual 6- and 8-protons. These fall within narrow ranges [δ(CDCl3) 6.07–6.24 and 6.30–6.47 respectively] devoid of overlap, which are useful for differentiating between 4,6- and 4,8-linked biflavanoids. Supplementary 1H-shift parameters are also available. The mechanism of a newly observed acid-catalysed migration of bromine from the 6- to the 8-position is examined. Direct carboxylation of (+)-catechin proceeds regiospecifically at the 6-position.

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