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Issue 11, 2003
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N-Acyl-5,5-dimethyloxazolidin-2-ones as latent aldehyde equivalents

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A study of the properties of N-hydrocinnamoyl- derivatives of 5,5-dimethyloxazolidin-2-one, 4,4-dimethyloxazolidin-2-one and oxazolidin-2-one upon hydride reduction with DIBAL-H demonstrates that the 5,5-dimethyl-group is essential for inhibition of endocyclic nucleophilic attack. For instance, treatment of N-hydrocinnamoyl-5,5-dimethyloxazolidin-2-one with DIBAL-H results in the selective formation of the stable N-1′-hydroxyalkyl derivative which may be regarded as a masked hydrocinnamaldehyde equivalent, as treatment under basic conditions affords the parent aldehyde in excellent yield. Treatment of N-hydrocinnamoyl-4,4-dimethyloxazolidin-2-one with DIBAL-H under identical conditions affords a complex mixture of products, including the formate ester product of endocyclic cleavage. As an alternate strategy, DIBAL-H reduction of straight chain and branched N-acyl-5,5-dimethyloxazolidin-2-one derivatives, followed by a Horner–Wadsworth–Emmons reaction affords α,β-unsaturated esters in good yields. Branching α- to the exocyclic carbonyl in N-acyl-oxazolidinones inhibits DIBAL-H reduction, but this can be overcome by precomplexation with ZnCl2, with subsequent fragmentation generating either the corresponding aldehyde or α,β-unsaturated esters. The addition of ZnCl2 has been shown to increase the diastereoselectivity observed in Wadsworth–Horner–Emmons reactions of lithiated phosphonates.

Graphical abstract: N-Acyl-5,5-dimethyloxazolidin-2-ones as latent aldehyde equivalents

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Publication details

The article was received on 30 Jan 2003, accepted on 03 Apr 2003 and first published on 17 Apr 2003

Article type: Paper
DOI: 10.1039/B301119D
Citation: Org. Biomol. Chem., 2003,1, 2001-2010
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    N-Acyl-5,5-dimethyloxazolidin-2-ones as latent aldehyde equivalents

    J. Bach, C. Blachère, S. D. Bull, S. G. Davies, R. L. Nicholson, P. D. Price, H. J. Sanganee and A. D. Smith, Org. Biomol. Chem., 2003, 1, 2001
    DOI: 10.1039/B301119D

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