Synthesis of cis-C-Iodo-N-Tosyl-Aziridines using Diiodomethyllithium: Reaction Optimization, Product Scope and Stability, and a Protocol for Selection of Stationary Phase for Chromatography

被引:28
作者
Boultwood, Tom [1 ]
Affron, Dominic P. [1 ]
Trowbridge, Aaron D. [1 ]
Bull, James A. [1 ]
机构
[1] Univ London Imperial Coll Sci Technol & Med, Dept Chem, London SW7 2AZ, England
基金
英国工程与自然科学研究理事会;
关键词
CATALYTIC ASYMMETRIC-SYNTHESIS; AMINO-ACID-DERIVATIVES; ONE-STEP PREPARATION; PRACTICAL SYNTHESIS; ALPHA-AMINO; ORGANOMETALLIC REAGENTS; CONVENIENT SYNTHESIS; ADDITION-REACTIONS; LITHIATION; BROMIDES;
D O I
10.1021/jo400956x
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The preparation of C-iodo-N-Ts-aziridines with excellent cis-diastereoselectivity has been achieved in high yields by the addition of diiodomethyllithium to N-tosylimines and N-tosylimine-HSO(2)Tol adducts. This addition-cyclization protocol successfully provided a wide range of cis-iodoaziridines, including the first examples of alkyl-substituted iodoaziridines, with the reaction tolerating both aryl imines and alkyl imines. An ortho-chlorophenyl imine afforded a beta-amino gem-diiodide under the optimized reaction conditions due to a postulated coordinated intermediate preventing cyclization. An effective protocol to assess the stability of the sensitive iodoaziridine functional group to chromatography was also developed. As a result of the judicious choice of stationary phase, the iodoaziridines could be purified by column chromatography; the use of deactivated basic alumina (activity IV) afforded high yield and purity. Rearrangements of electron rich aryl-iodoaziridines have been promoted, selectively affording either novel alpha-iodo-N-Ts-imines or alpha-iodo-aldehydes in high yield.
引用
收藏
页码:6632 / 6647
页数:16
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