Skip to main content

Official Journal of the Japan Wood Research Society

  • Original Article
  • Published:

Absolute configuration of arylglycerol-β-aryl ethers obtained by asymmetric reduction of the correspondingα-ketonic compound with intactFusarium solani cells


When (±)-α-oxo-guaiacylglycerol-β-(vanillic acid) ether (1) is degraded byFusarium solani M-13-1, theα-ketone is initially reduced to giveerythro andthreo guaiacylglycerol-β-(vanillic acid) ethers (2), arylglycerol-β-aryl ethers, both of which are enantiomerically pure. The absolute configuration in each2 was determined by Mosher's method; the products were converted toα,γ-di-(R)-α-methoxy-α-trifluoromethylphenylacetates (MTPA esters) (3′) oferythro (-)- andthreo (+)-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 synthesizederythro (±)-3 andthreo (±)-3. To assign theα- andγ-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 Δδ 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 Δδ values ofα-MTPA-OCH3 were larger than those ofγ-MTPA-OCH3 owing to a shielding effect of the veratryl ring located on theα-MTPA-OCH3, and that theα-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 catabolicerythro 3′ [fromerythro (-)-3] andthreo 3′ [fromthreo (+)-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 theα-ketone fromre-face of both (βR)-1 and (βS)-1, givingerythro (αS, βR)-2 andthreo (αS, βS)-2, respectively.


  1. Katayama T, Sogo M, Higuchi T (1986) Degradation and stereoselective reduction of anα-ketone derivative of guaiacylglycerol-β-vanillin ether, a lignin substructure model, byFusarium solani M-13-1. Holzforschung 40:175–182

    Article  CAS  Google Scholar 

  2. Katayama T, Sogo M (1989) An optically-active compound formed by the reduction of anα-ketonic lignin substructure model compound byFusarium solani M-13-1. Mokuzai Gakkaishi 35:1116–1124

    CAS  Google Scholar 

  3. Dale JA, Dull DL, Mosher HS (1969)α-Methoxy-α-trifluoromethylphenylacetic acid, a versatile reagent for the determination of enantiomeric composition of alcohols and amines. J Org Chem 34:2543–2549

    Article  CAS  Google Scholar 

  4. Dale JA, Mosher HS (1973) Nuclear magnetic resonance enantiomer reagents. Configuration correlations via nuclear magnetic resonance chemical shifts of diastereomeric mandelate,O-methylmandelate, andα-methoxy-α-trifluoromethylphenylacetate (MTPA) esters. J Am Chem Soc 95:512–519

    Article  CAS  Google Scholar 

  5. Yamaguchi S (1985) The determination methods of chirality with NMR (in Japanese). Chem Today 168(3):14–21

    CAS  Google Scholar 

  6. Matsuda N, Kikuchi M (1996) Studies on the constitution ofLonicera species. X. Neolignan glycosides from the leaves ofLonicera gracilipes var.glandulosa Maxim. Chem Pharm Bull (Tokyo) 44:1676–1679

    Article  CAS  Google Scholar 

  7. Adler E, Eriksoo E (1955) Guaiacylglycerol and itsβ-guaiacyl ether. Acta Chem Scand 9:341–342

    Article  CAS  Google Scholar 

  8. Miksche GE (1973) Zum alkalischen Abbau von Arylglycerin-β-(2,6-dimethoxy-4-alkylaryl)-ätherstrukturen (in German). Acta Chem Scand 27:1355–1368

    Article  CAS  Google Scholar 

  9. King LC, Ostrum GK (1964) Selective bromination with copper (II) bromide. J Org Chem 29:3459–3461

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations


Corresponding author

Correspondence to Takeshi Katayama.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Katayama, T., Tsutsui, J., Tsueda, K. et al. Absolute configuration of arylglycerol-β-aryl ethers obtained by asymmetric reduction of the correspondingα-ketonic compound with intactFusarium solani cells. J Wood Sci 46, 458–465 (2000).

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI:

Key words