On the Mechanism of the Stevens Rearrangement

Abstract

The reaction mechanism for the Stevens rearrangement is one of the most controversial reaction mechanisms in organic chemistry. This account will address that controversy reviewing the experimental as well as some computational results.

1 Introduction

2 Evolution of the Mechanistic Knowledge

2.1 Stevens (1928)

2.2 Stevens (1930)

2.3 Stevens (1932)

2.4 Campbell (1946)

2.5 Hauser (1951)

2.6 Kline (1952)

2.7 Lepley (1969)

2.8 Baldwin (1970)

3 Computational Investigations

4 [2,3]-Stevens Rearrangement?

5 Conclusion

Key words

Stevens rearrangement - [1,2]-shift - ammonium ylide - Sommelet–Hauser rearrangement - mechanistic investigations

• References

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• 1b Stevens TS. J. Chem. Soc. 1930; 2107
• 1c Stevens TS, Snedden WW, Stiller ET, Thomson T. J. Chem. Soc. 1930; 2119
• 1d Thomson T, Stevens TS. J. Chem. Soc. 1932; 55
• 1e Thomson T, Stevens TS. J. Chem. Soc. 1932; 69
• 1f Dunn JL, Stevens TS. J. Chem. Soc. 1932; 1926
• 1g Thomson T, Stevens TS. J. Chem. Soc. 1932; 1932
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• 1i Bamford WR, Stevens TS, Wright JW. J. Chem. Soc. 1952; 4334
• 2 For the latest review on synthetic applications, see: Vanecko JA, Wan H, West FG. Tetrahedron 2006; 62: 1043 ; and references cited therein
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• 7 (–)-Hydratopic acid (29, Scheme 9) was converted into (–)-1-phenylethylamine by Hofmann rearrangement of the corresponding amide: Arcus, C. L., Kenyon, J. J. Chem. Soc. 1939, 916.
• 8 Lepley AR. J. Am. Chem. Soc. 1969; 91: 1237
• 9 For simple explanation of this phenomenon, see: Goez M. Concepts Magn. Reson. 1995; 7: 69
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• 14 One reviewer has suggested that it might be simply called ‘[2,3]-sigmatropic rearrangement’ as this type of transformation was not discovered by these chemists. While I do not dispute the fact that this rearrangement (54 → 57, Scheme 13) predates both Sommelet and Hauser, referring to it as ‘the allyl-Sommelet–Hauser rearrangement’ would emphasize the fact that it has nothing in common with the controversial Stevens [1,2]-shift