Synthesis, resolution, and absolute stereochemistry of (-)-blestriarene C

Tetsutaro Hattori, Yuhi Shimazumi, Hitoshi Goto, Osamu Yamabe, Naoya Morohashi, Wataru Kawai, Sotaro Miyano

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43 Citations (Scopus)

Abstract

A naturally occurring 1,1′-biphenanthrene, blestriarene C (1), was prepared in 13 steps and 30% overall yield. The key steps are the ester-mediated nucleophilic aromatic substitution on 2,6-ditert-butyl-4-methoxyphenyl 5-isopropoxy-2-methoxybenzoate (4) by 2-methoxy-4-methoxymethoxy-6-methylphenylmagnesium bromide (5) and a novel intramolecular cyclization of the resulting 4-isopropoxy-2′-methoxy-4′-methoxymethoxy-6′ -methylbiphenyl-2-carboxylic ester 14 to 7-isopropoxy-4-methoxy-2-(methoxymethoxy)phenanthren-9-ol (15). The racemic blestriarene C was optically resolved by chiral HPLC on a preparative scale to give several 10-mg yields of both the enantiomers in up to 95% ee. The absolute stereochemistry was determined to be Sa-(-) by the axial chirality recognition method, which was based on the stereospecific formation of a 12-membered cyclic diester containing two biaryl-o,o′-diyl unites joined by ester -CO2- linkages. The validity of the method was confirmed by an X-ray crystallographic analysis and ab initio conformational analyses of such 12-membered cyclic diesters. It was found that blestriarene C and its 7,7′-diisopropyl ether 2 underwent rapid photoracemization even under ambient light exposure.

Original languageEnglish
Pages (from-to)2099-2108
Number of pages10
JournalJournal of Organic Chemistry
Volume68
Issue number6
DOIs
Publication statusPublished - 2003 Mar 21

ASJC Scopus subject areas

  • Organic Chemistry

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