Condensed Tannins Proanthocyanidins, 44 from Leucoanthocyanidins Flavan-3,4-diols

Biosynthesis of Flavan-3-ols (40) and Condensed Tannins (Proanthocyanidins, 44) from Leucoanthocyanidins (Flavan-3,4-diols, 37)... 

Flavanols and procyanidins Flavanols, or flavan-3-ols, are synthesized via two routes, with (+) catechins formed from flavan-3,4-diols via leucoanthocyanidin reductase (LAR), and (—) epicatechins from anthocyanidins via anthocyanidin reductase (ANR) (see Fig. 5.4). These flavan-3-ol molecules are then polymerized to condensed tannins (proanthocyanidins or procyanidins), widely varying in the number and nature of their component monomers and linkages (Aron and Kennedy 2008 Deluc and others 2008). It is still not known whether these polymerization reactions happen spontaneously, are enzyme catalyzed, or result from a mixture of both. 

Flavan-3,4-diols FIavan-3,4-diols, also known as leucoanthocyanidins, are not particularly prevalent in the plant kingdom, instead being themselves precursors of flavan-3-ols (catechins), anthocyanidins, and condensed tannins (proanthocyanidins) (see Fig. 5.4). Flavan-3,4-diols are synthesized from dihydroflavonol precursors by the enzyme dihydroflavonol 4-reductase (DFR), through an NADPH-dependent reaction (Anderson and Markham 2006). The substrate binding affinity of DFR is paramount in determining which types of downstream anthocyanins are synthesized, with many fruits and flowers unable to synthesize pelargonidin type anthocyanins, because their particular DFR enzymes cannot accept dihydrokaempferol as a substrate (Anderson and Markham 2006). 

Flavanol oligomers and polymers are also called condensed tannins or proan-thocyanidins. The term tannin refers to their capacity to interact or react with proteins and precipitate them out. When heated under acidic conditions, these molecules release red anthocyanidin pigments, hence the term proanthocyanidins. The term leucoanthocyanidin, also referring to this particular property, is sometimes encountered in the literature. However, this should be restricted to another group of compounds, flavan 3,4-diols, which are intermediates in the biosynthetic pathway leading to flavanols and anthocyanins (Stafford and Lester 1984 Nakajima et al. 2001 Abrahams et al. 2003) but have never been isolated from grapes, presumably due to their instability. 

Although earlier reviews by Haslam (134-136) discuss the many problems that have arisen about the systematic classification and nomenclature of proanthocyanidins, it seems useful to repeat the definition of the term proanthocyanidin as initially established by Freudenberg and Weinges (116) - the proanthocyanidins are all the colorless substances isolated from plants which, when treated with acid, form anthocyanidins. Thus the leucoanthocyanidins (now restricted to the flavan-3,4-diols), the condensed tannins (Sect. 7.7), and any other colorless flavonoid derivatives that produce anthocyanidins on heating with acid should be grouped under this class of compounds. 

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