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- Title
Absolute configuration of arylglycerol- β-aryl ethers obtained by asymmetric reduction of the corresponding α-ketonic compound with intact Fusarium solani cells.
- Authors
Katayama, Takeshi; Tsutsui, Jyoji; Tsueda, Kazuo; Miki, Takao; Yamada, Yasuhiro; Sogo, Murao
- Abstract
When (±)- α-oxo-guaiacylglycerol- β-(vanillic acid) ether ( 1) is degraded by Fusarium solani M-13-1, the α-ketone is initially reduced to give erythro and threo guaiacylglycerol- β-(vanillic acid) ethers ( 2), arylglycerol- β-aryl ethers, both of which are enantiomerically pure. The absolute configuration in each 2 was determined by Mosher's method; the products were converted to α,γ-di-( R)- α-methoxy- α-trifluoromethylphenylacetates (MTPA esters) (3′) of erythro (-)- and threo (+)-veratrylglycerol- β-(methyl vanillate) ethers ( 3), whose1H nuclear magnetic resonance (NMR) spectra were examined and compared with those of four di-( R)-MTPA ester ( 3′) diastereomers from chemically synthesized erythro (±)- 3 and threo (±)- 3. To assign the α- and γ-MTPA-OCH3 peaks, the1H NMR scans of several compounds that have substructures of 3′ and their 3,4,5-trimethoxyphenyl analogues were examined. When a racemic alcohol reacts with ( R)-MTPA to give a pair of ( R)-MTPA ester diastereomers, the Δ δ value was defined as the absolute value of the difference in the1H chemical shifts of the peak between the diastereomers. It was found that the Δ δ values of α-MTPA-OCH3 were larger than those of γ-MTPA-OCH3 owing to a shielding effect of the veratryl ring located on the α-MTPA-OCH3, and that the α-MTPA-OCH3 peaks in the 3,4,5-trimethoxyphenyl compounds shifted downfield relative to those in the veratryl compounds. On the basis of the1h NMR data of ( R)-MTPA esters, the absolute configuration of the four chemically prepared diastereomers ( 3′) were determined. The catabolic erythro 3′ [from erythro (-)-3] and threo 3′ [from threo (+)- 3] were identical to ( R, αS, βR)-erythro 3′ and ( R, αS, βS)- threo 3′, respectively. An hydrogen species in the fungal reduction would attack the α-ketone from re-face of both ( βR)- 1 and ( βS)- 1, giving erythro ( αS, βR)- 2 and threo (αS, βS)- 2, respectively.
- Publication
Journal of Wood Science, 2000, Vol 46, Issue 6, p458
- ISSN
1435-0211
- Publication type
Article
- DOI
10.1007/BF00765804