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

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

Key words

rearrangements - vinylaziridines - ylides - pericyclic reactions - asymmetric reactions

References and Notes

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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Somfai P., unpublished results.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Ottosson H., Somfai P., unpublished results.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.