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

被引:20
作者
Bach, J [1 ]
Blachère, C [1 ]
Bull, SD [1 ]
Davies, SG [1 ]
Nicholson, RL [1 ]
Price, PD [1 ]
Sanganee, HJ [1 ]
Smith, AD [1 ]
机构
[1] Univ Oxford, Dyson Perrins Lab, Oxford OX1 3QY, England
关键词
D O I
10.1039/b301119d
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
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 alpha, beta-unsaturated esters in good yields. Branching alpha- to the exocyclic carbonyl in N-acyl-oxazolidinones inhibits DIBAL-H reduction, but this can be overcome by precomplexation with ZnCl(2), with subsequent fragmentation generating either the corresponding aldehyde or alpha, beta-unsaturated esters. The addition of ZnCl(2) has been shown to increase the diastereoselectivity observed in Wadsworth-Horner-Emmons reactions of lithiated phosphonates.
引用
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页码:2001 / 2010
页数:10
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