Application of the silicon-tether strategy for controlling the regioselectivity and diastereoselectivity of intramolecular nitrone cycloadditions for aminopolyol synthesis

被引:32
作者
Ishikawa, T [1 ]
Kudo, T [1 ]
Shigemori, K [1 ]
Saito, S [1 ]
机构
[1] Okayama Univ, Fac Engn, Dept Biosci & Biotechnol, Okayama 7008530, Japan
关键词
D O I
10.1021/ja000248o
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Highly regioselective and diastereoselective intramolecular chiral nitrone cycloaddition reactions with a vinyl group tethered by a silicon atom have been developed as a general method for the synthesis of stereodefined amino polyols. This strategy features a series of one-pot reactions involving (1) DIBAH reduction of the carbonyl groups of chiral alpha- or -beta-hydroxy carbonyl compounds, in which the hydroxy group is protected as diphenylvinylsilyl ethers, at -78 degrees C to give an aldehyde, (2) condensation of the aldehyde with N-benzylhydroxylamine to furnish nitrone (-78 degrees C --> rt), and (3) intramolecular [3 + 2] dipolar cycloaddition reaction between the nitrone and the silicon-tethered vinyl group (rt --> 70 degrees C, 3-15 h) to give isoxazolidine derivatives as direct precursors for amino polyols. Since the cycloaddition reaction is concerted in nature and passes through a fused-bicyclic transition state, the substituents, the nitrone substrate, and the silicon atom bias the stereochemical course of this addition, resulting in highly diastereoselective and synthetically useful transformations.
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页码:7633 / 7637
页数:5
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