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Issue 3, 2010
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The thio-adduct facilitated, enzymatic kinetic resolution of 4-hydroxycyclopentenone and 4-hydroxycyclohexenone

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Abstract

The addition of 3,4-dimethoxybenzyl thiol 8, as a benzyl thiol surrogate, to racemic 4-hydroxycyclopent-2-enone 2 and 4-hydroxycyclohex-2-enone 15 gave the corresponding cis-adducts (±)-3-(3,4-dimethoxybenzylthio)-4-hydroxycyclopentanone 4b and (±)-3-(3,4-dimethoxybenzylthio)-4-hydroxycyclohexanone 16 with good diastereocontrol. In both cases, subsequent treatment with vinyl acetate, in the presence of a lipase enabled enantiomer resolution. Thus, (+)-16 and the acetate of its enantiomer, (–)-(1R,2S)-2-(3,4-dimethoxybenzylthio)-4-oxocyclohexyl acetate, (–)-17 were isolated in 98% enantiomeric excess. Based on the 1,4-dioxygenation pattern, (–)-17 can be used to prepare both enantiomers of 4-(tert-butyldimethylsilyloxy)cyclohex-2-enone 19. Firstly, saponification, with a sub-stoichiometric amount of NaOMe, followed by a one-pot silyl ether formation–sulfide elimination sequence gave (+)-19. Then using the same starting material a 6-step sequence, featuring a diastereoselective NaBH4 reduction and a Cope-type sulfoxide elimination, gave (–)-19.

Graphical abstract: The thio-adduct facilitated, enzymatic kinetic resolution of 4-hydroxycyclopentenone and 4-hydroxycyclohexenone

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Publication details

The article was received on 11 Aug 2009, accepted on 31 Oct 2009 and first published on 30 Nov 2009


Article type: Paper
DOI: 10.1039/B916506A
Org. Biomol. Chem., 2010,8, 539-545

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    The thio-adduct facilitated, enzymatic kinetic resolution of 4-hydroxycyclopentenone and 4-hydroxycyclohexenone

    A. O'Byrne, C. Murray, D. Keegan, C. Palacio, P. Evans and B. S. Morgan, Org. Biomol. Chem., 2010, 8, 539
    DOI: 10.1039/B916506A

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