Enantioselective syntheses of 2-deoxyxylono-1,4-lactone and 2-deoxyribono-1,4-lactone from 1,3-dioxan-5-yl diazoacetates

被引:39
作者
Doyle, MP [1 ]
Tedrow, JS [1 ]
Dyatkin, AB [1 ]
Spaans, CJ [1 ]
Ene, DG [1 ]
机构
[1] Univ Arizona, Dept Chem, Tucson, AZ 85721 USA
关键词
D O I
10.1021/jo991211t
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
1,3-Dioxan-5-yl diazoacetates are valuable substrates for highly diastereoselective and enantio-selective carbon-hydrogen insertion reactions. trans-2-(tert-Butyl)-1,3-dioxan-5-yl diazoacetate is a direct precursor to 2-deoxyribono-1,4-lactone in up to 81% ee, whereas cis-2-(tert-butyl)-1,3-dioxan-5-yl diazoacetate yields only the protected 2-deoxyxylono-1,4-lactone in up to 96% ee. However, trans-2-aryl-1,3-dioxan-5-yl diazoacetate (aryl = phenyl or 2-naphthyl) forms the precursor to 2-debxyxylono-1,4-lactone in up to 95% ee but with the mirror image configuration of that produced from the trans-2-(tert-butyl) analogue. The catalysts that are most suitable for these carbon-hydrogen insertion reactions are chiral dirhodium(II) carboxamidates. 1,3-Dialkoxy-2-propyl diazoacetates give mainly 2-deoxyxylono-1;4-lactone derivatives (>90:10) with generally high enantiocontrol, but replacement of hydrogen at the 2-position of these 2-propyl diazoacetates led to a mixture of products.
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页码:8907 / 8915
页数:9
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