Aminolysis of Vinyl Epoxides as an Efficient Entry to N-H Vinylaziridines

Ulf M. Lindström; Peter Somfai

doi:10.1055/s-1998-2004

Synthesis 1998; 1998(1): 109-117
DOI: 10.1055/s-1998-2004

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Aminolysis of Vinyl Epoxides as an Efficient Entry to N-H Vinylaziridines

Ulf M. Lindström^* , Peter Somfai

^*Organic Chemistry 2, Center of Chemistry and Chemical Engineering, Lund Institute of Technology, Lund University, P.O. Box 124, S-221 00 Lind, Sweden; Fax + 46(46)2 22 82 09; E-mail: peter.somfai@orgk2.lth.se

Abstract

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Vinyl epoxides 8 a - f, 11 and 12 have been prepared from the corresponding epoxy alcohols while 8 g was formed by a regioselective epoxidation of the parent diene. Aminolysis of these materials resulted in a regio- and stereoselective nucleophilic opening at C3 in good yields except for the sterically hindered substrates. The trans-oxiranes gave the anti-amino alcohols while the cis derivative 12 gave the syn isomer 17. Cyclization of the anti-amino alcohols was best effected using the Mitsunobu protocol giving the corresponding N-H vinylaziridines in 50-54% yields, while the syn-amino alcohol 17 was transformed into the cis-vinylaziridine 31 with chlorosulfonic acid followed by base treatment in 20% yield. The outcome of these cyclizations seems to indicate that they are controlled by subtle steric effects in the substrate. The N-H vinylaziridine 24 was alkylated with tert-butyl bromoacetate and the product subjected to an aza-[2,3]-Wittig rearrangement to give tetrahydropyridine 30 while acetylation of 24 followed by base treatment resulted in an aza-[3,3]-Claisen rearrangement yielding the seven-membered lactam 32.

vinyl epoxides - vic-amino alcohols - cyclization - vinylaziridines

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