Synlett 2007(8): 1190-1202  
DOI: 10.1055/s-2007-980341
ACCOUNT
© Georg Thieme Verlag Stuttgart · New York

Investigations of the [2,3]-Sigmatropic Rearrangements of Vinylaziridines and Allylic Amines

Peter Somfai*, Olaf Panknin*
KTH Chemical Science and Engineering, Organic Chemistry, 10044 Stockholm, Sweden
Fax: +46(8)7912333; e-Mail: somfai@kth.se;
Weitere Informationen

Publikationsverlauf

Received 4 October 2006
Publikationsdatum:
08. Mai 2007 (online)

Abstract

This account summarizes our studies of [2,3]-sigma­tropic rearrangements of vinylaziridines and allylic amines. The scope and limitations of the reactions as well as our present mechanistic understanding are also discussed.

1 Introduction

2 Aza-[2,3]-Wittig Rearrangement of Vinylaziridines

2.1 Early Attempts

2.2 Synthesis of Vinylaziridines

2.3 Rearrangement of Vinylaziridines

2.4 Total Synthesis of Indolizidines (-)-209B and (-)-209D

3 [2,3]-Sigmatropic Rearrangement of Allylic Amines

3.1 Lewis Acid Mediated Rearrangements

3.2 Asymmetric Rearrangements

4 Conclusions

20

Somfai P., unpublished results.

21

Ottosson H., Somfai P., unpublished results.

32

InCl3 and ZnCl2 gave low yields; other unsuccessful Lewis acids were CuCl, CuCl2, TiCl4, Yb(OTf)3, FeCl3, ZrCl2Cp2, and ScCl3.

40

PhMe: 70% yield, er ≥ 98.5:1.5; Et2O: 27% yield,
er ≥ 98.5:1.5; THF: 15% yield, er = 92:8.