STEREOCHEMISTRY OF ERYTHRO- AND THREO-SYRINGYLGLYCEROL-8-O-4'-(SINAPYL ALCOHOL) ETHERS AND THEIR ENZYMATIC FORMATION WITH OPTICAL ACTIVITY IN EUCOMMIA ULMOIDES

Md. Shameul Alam; Deeder Sultana; Toshisada Suzuki; Takeshi Katayama

doi:10.9755/ejfa.v22i6.4661

Authors

Md. Shameul Alam Faculty of Agriculture, Kagawa University, Miki-cho, Kita-gun, Kagawa 761-0795, Japan; 2 Faculty of Medicine, Kagawa University, Miki-cho, Kita-gun, Kagawa 761-0793, Japan
Deeder Sultana Faculty of Medicine, Kagawa University, Miki-cho, Kita-gun, Kagawa 761-0793, Japan
Toshisada Suzuki Faculty of Agriculture, Kagawa University, Miki-cho, Kita-gun, Kagawa 761-0795, Japan;
Takeshi Katayama Faculty of Agriculture, Kagawa University, Miki-cho, Kita-gun, Kagawa 761-0795, Japan;

DOI:

https://doi.org/10.9755/ejfa.v22i6.4661

Keywords:

Stereochemistry, SGSE, erythro, threo, MTPA, soluble enzyme, Eucommia ulmoides

Abstract

In this study an enzymatic system, horseradish peroxidase (HRP)-hydrogen peroxide was used as catalysts for the enzymatic formation of enantiospecific syringulglycerol-8-O-4? (sinapyl alcohol) ethers (SGSEs) from enzyme preparations of Eucommia ulmoides with sinapyl alcohol (SA) as a monolignol precursor. Reversed phase HPLC analysis of the erythro- and threo-SGSE showed that the ratio of erythro: threo was 47: 53. Both isomers were isolated by HPLC and their structural confirmation was done by 1H NMR spectra. Chiral column HPLC analysis of the erythro- and threo-SGSE showed that their enantiomeric compositions were as follows: (+)-erythro: (-)-erythro = 46.7:53.3 (6.6% e.e), and (+)-threo: (-)-threo = 45.2: 54.8 (9.6% e.e). To elucidate the stereochemistry of erythro and threo- SGSEs, we have determined absolute configurations of the four stereoisomers, (+)-erythro-, (-)-erythro-, (+)-threo-, and (-)-threo-SGSEs as (7R, 8S), (7S, 8R), (7S, 8S), and (7R, 8R), respectively, by Mosher's method through the 1H NMR spectroscopy of (+)-(R)-?-methoxy- ?- trifluoromethylphenylacetate (MTPA) esters of ?, ? and ?' positions.