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Synthesis 2009(11): 1886-1896  
DOI: 10.1055/s-0028-1088077
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Application of Phenolate Ion Mediated Intramolecular Epoxide Ring Opening in the Enantioselective Synthesis of Functionalized 2,3-Dihydrobenzofurans and 1-Benzopyrans [¹]

Subal Kumar Dinda, Sajal Kumar Das, Gautam Panda*
Medicinal and Process Chemistry Division, Central Drug Research Institute, Lucknow 226001, UP, India
Fax: +91(522)2223405; e-Mail: gautam.panda@gmail.com;
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Publication History

Received 21 January 2009
Publication Date:
27 April 2009 (online)

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Abstract

The enantioselective synthesis of 2-isopropenyl-2,3-dihydrobenzofurans, 4-(2,3-dihydrobenzofuran-2-yl)-2-methylbut-3-en-2-ols, 2-hydroxymethyl chromans, and 4-chroman-2-yl-2-methylbut-3-en-2-ols has been achieved using Sharpless asymmetric epoxidation-derived enantiomerically enriched epoxy alcohols as chiral building blocks. A phenolate ion mediated intramolecular epoxide ring-opening reaction was the key step for every cyclization reaction.

Key words

2-isopropenyl-2,3-dihydrobenzofuran - 2-hydroxy­methyl chromans - epoxidation - epoxides - polycycles - ring opening

1

CDRI communication number 7184.

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1

CDRI communication number 7184.

23

The enantiomeric excess values were determined by converting the epoxy alcohols into their Mosher ester derivatives and analyzing the ¹H NMR spectra of the corresponding Mosher esters.

24

In the tosylation reaction of 24a,b, formation of minor amount of the corresponding ditosylated products was also observed and these undesired products were eliminated by column chromatography.

25

The enantiomeric excess values of 27a,b were determined by chiral HPLC analysis.

29

The enantiomeric excess values of 38a,b were determined by chiral HPLC analysis (Chiral Cel OD, petroleum ether (bp 30-60 ˚C)-i-PrOH (98:2) 1 mL/min, 254 mm.