The asymmetric synthesis of 2-benzopyrans and their quinones through intramolecular diastereoselective ring-closure of titanium phenolates of phenolic aldehydes

Giles, R.G.F. and Joll, C.A. (1999) The asymmetric synthesis of 2-benzopyrans and their quinones through intramolecular diastereoselective ring-closure of titanium phenolates of phenolic aldehydes. Journal of the Chemical Society, Perkin Transactions 1 (20). pp. 3039-3048.

Abstract

Treatment of the phenolic aldehyde (α′S,2S )-2-(5′-hydroxy-2′-methoxy-α′-methylbenzyloxy)propanal 15 with titanium tetraisopropoxide followed by ultrasonication led to its completely diastereoselective cyclisation in high yield to afford (1S,3S,4R)-3,4-dihydro-1,3-dimethyl-8-methoxy-2-benzopyran-4,5-diol 18, which was characterised as its more stable 4,5-diacetate 19. The diastereomeric (α′R,2S )-2-(5′-hydroxy-2′-methoxy-α′-methylbenzyloxy)propanal 17 on similar treatment gave rise to a mixture of (1R, 3S, 4R)- and (1R, 3S, 4S )-3,4-dihydro-1,3-dimethyl-8-methoxy-2-benzopyran-4,5-diols 21 and 23, isolated as the 4,5-diacetates 22 and 24, in a ratio of 3∶1. Oxidative dealkylation of the diol 18 with silver(II) oxide afforded (1S,3S,4R)-3,4-dihydro-1,3-dimethyl-4-hydroxy-2-benzopyran-5,8-quinone 2 in high yield, while the epimeric 1R quinone 40 was similarly obtained from diol 21.

Item Type:	Journal Article
Murdoch Affiliation(s):	School of Chemical and Mathematical Science
Publisher:	Royal Society of Chemistry
Copyright:	© 1999 Royal Society of Chemistry
URI:	http://researchrepository.murdoch.edu.au/id/eprint/35537

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