Asymmetric Syntheses of (−)-ADMJ and (+)-ADANJ: 2-Deoxy-2-amino Analogues of (−)-1-Deoxymannojirimycin and (+)-1-Deoxyallonojirimycin
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- 作者：Stephen G. Davies ; Aude L. A. Figuccia ; Ai M. Fletcher Paul ; M. Roberts ; James E. Thomson
- 刊名：Journal of Organic Chemistry
- 出版年：2016
- 出版时间：August 5, 2016
- 年：2016
- 卷：81
- 期：15
- 页码：6481-6495
- 全文大小：749K
- 年卷期：0
- ISSN：1520-6904
文摘
The asymmetric syntheses of (−)-ADMJ and (+)-ADANJ, the 2-deoxy-2-amino analogues of (−)-1-deoxymannojirimycin and (+)-1-deoxyallonojirimycin, are described herein. Methodology for the ring-closing iodoamination of bishomoallylic amines followed by in situ ring-expansion (via intramolecular ring-opening of the corresponding aziridinium intermediates with a tethered carbamate moiety) to give oxazolidin-2-ones was initially optimized on a model system. Subsequent application of this methodology to two enantiopure bishomoallylic amines (which were produced via aminohydroxylation of an α,β-unsaturated ester, partial reduction, and reaction of the corresponding aldehyde with vinylmagnesium bromide) also proceeded with concomitant N-debenzylation to afford the corresponding diastereoisomerically pure (>99:1 dr) oxazolidin-2-ones. Subsequent deprotection of these enantiopure templates gave (−)-ADMJ and (+)-ADANJ as single diastereoisomers in 16% and 24% overall yield, respectively.