Logo image
The asymmetric synthesis of 2-benzopyrans and their quinones through intramolecular diastereoselective ring-closure of titanium phenolates of phenolic aldehydes
Journal article   Peer reviewed

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

R.G.F. Giles and C.A. Joll
Journal of the Chemical Society, Perkin Transactions 1, (20), pp.3039-3048
1999
url
Link to Published Version *Subscription may be requiredView

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.

Details

Metrics

16 Record Views
Logo image