HYDROLYZABLE TANNIN STRUCTURAL CHEMISTRY
Hydrolyzable tannins are
derivatives of gallic acid (3, 4, 5-trihydroxyl benzoic acid). Gallic acid is
esterified to a core polyol, and the galloyl groups may be further esterified
or oxidatively crosslinked to yield more complex hydrolysable tannins.
Early work on hydrolyzable
tannins included Haslam’s significant elucidations of the structures of the
simple gallotannins (Haslam, E. Plant polyphenols. Vegetable tannins
revisited, ed.; Cambridge University Press: Cambridge, U. K., 1989). More
recently, Okuda et al.(Okuda, T.; Yoshida, T.; Hatano, T. Hydrolyzable tannins
and related polyphenols. Progress in the Chemistry of Organic Natural
Products 1995, 66, 1-117) have been particularly active in characterization
and classification of complex hydrolyzable tannins. Feldman’s synthetic work (Feldman
KS, Lawlor MD, and Sahasrabudhe K Ellagitannin chemistry. Evolution of a
threecomponent coupling strategy for the synthesis of the dimeric ellagitannin
coriariin A and a dimeric gallotannin analogue. 2000; 8011-9) has provided
useful insights into likely biosynthetic routes for the complex hydrolyzable
tannins. A limited survey of structures and their relationships is provided
here.
Gallotannins.
The simplest hydrolyzable
tannins, the gallotannins, are simple polygalloyl esters of glucose.
The prototypical gallotannin is
pentagalloyl glucose (β-1,2,3,4,6-Pentagalloyl-O-DGlucopyranose). Pentagalloyl glucose, or PGG, has five identical ester
linkages that involve aliphatic hydroxyl groups of the core sugar. The alpha
anomer is not common in nature.
Like all of the gallotannins, PGG
has many isomers. The molecular weights of all the isomers of PGG are the same
(940 g/mol), but chemical properties such as susceptibility to hydrolysis and chromatographic behavior; and biochemical properties such as ability to precipitate
protein; are structure-dependent.
The polygalloyl ester chains
found in gallotannins are formed by either meta- or para-depside bonds,
involving a phenolic hydroxyl rather than an aliphatic hydroxyl group. The
depside bond is more easily hydrolyzed than an aliphatic ester bond. Methanolysis in weak acid in
methanol breaks
depside but not ester bonds. Thus the core polyol with its esterified galloyl
groups can be produced from complex mixtures of polygalloyl esters by
methanolysis with acetate buffer. Strong mineral acid, heat and methanol can be used to methanolzye both
despide and ester bonds yielding the core polyol and methyl gallate. Hydrolysis with strong acid converts gallotannins to gallic
acid and the core polyol.
Simple gallotannins with up to 12
esterifed galloyl groups and a core glucose are routinely found in tannins from
sumac or oak galls. Commercial tannic acid is comprised of mixtures of gallotannins
from sumac (Rhus semialata) galls (Chinese gallotannin); Aleppo oak (Quercus
infectoria) galls (Turkish gallotannin); or sumac (R. coriaria, R.
typhina) leaves (sumac gallotannin). Although commercial sources provide a
nominal molecular weight for tannic acid (1294 g/mol), the preparations are
heterogeneous and variable mixtures of galloyl esters. Tannic acid is not an
appropriate standard for any tannin analysis because of its poorly defined composition.
PGG can be prepared from some commercial tannic acids
by methanolysis in acetate buffer. For the preparation to be successful, the
tannic acid must have PGG as its core ester, most likely in preparations of Chinese
or sumac gallotannin. Turkish gallotannin is comprised of esters of 1,2,3,6-tetragalloyl
glucose; or 1,3,4,6-tetragalloyl glucose.
Although for many gallotannins glucose is the
alcohol, other polyols including glucitol; hammamelose; shikimic acid; quinic
acid; and quercitol; have been reported as constitutents of gallotannins from a
few species. For example, aceritannin is found in leaves of several specie
of maple (Acer), and hamamelitannin is found
in bark of witch hazel (Hamamelis virginiana), oak (Quercus rubra),
and several chestnut species (Castanea sp.).
Ellagitannins.
Oxidative coupling of galloyl
groups converts gallotannins to the related ellagitannins. The simple
ellagitannins are esters of hexahydroxydiphenic acid (HHDP). HHDP spontaneously
lactonizes to ellagic
acid in aqueous
solution
Intramolecular carbon-carbon coupling to form
HHDP is most common between C-4/C-6 (e.g. eugeniin); and C-2/C-3 (e.g.
casuarictin, also has C-4/C-6), as would be expected for polygalloyl glucoses
in the more stable 4C1 conformation. However, in a few plants
intramolecular coupling
occurs at C-3/C-6 (e.g. corilagin), C-2/C-4
(e.g. geraniin, also has C-3/C-6), or C-1/C-6 (e.g. davidiin), suggesting the
polygalloyl glucose starting material was in the less stable1C4
conformation. Geraniin is further
characterized by partial oxidation of the C-2/C-4 HHDP to dehydro-HHDP, and in
aqueous solution several forms of dehydro-HHDP can be detected in geraniin by
nmr.
In some plants including oak and chestnut the
ellagitannins are further elaborated via ring opening. Thus after conversion of
casuarictin to pedunculagin, the pyranose ring of the glucose opens and the
family of compounds including casuariin, casuarinin, castalagin, and castlin; stachyurin,
vescalagin and vescalin forms.
The ellagitannins can undergo intermolecular
oxidative coupling with other hydrolysable tannins to yield dimers. For
example, in several euforbs (e.g. Euphorbia watanabei) geraniin oxidatively
condenses with PGG to yield various euphrobins, characterized by the valoneoyl
group.
Oenothein B, Woodfordin C, Cuphiin D1 and
Eugeniflorin D1 are macrocyclic dimers linked by two valoneoyl groups, and the
nobotanins are macrocyclic trimers.
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