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Synthesis 2020; 52(01): 21-26
DOI: 10.1055/s-0039-1690682
DOI: 10.1055/s-0039-1690682
short review
On the Mechanism of the Stevens Rearrangement
Financial support from Natural Sciences and Engineering Research Council of Canada (NSERC) and Brock University Graduate Studies (Research Fellowships to DB) is appreciated.Further Information
Publication History
Received: 22 July 2019
Accepted after revision: 29 August 2019
Publication Date:
13 September 2019 (online)
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
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References
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- 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
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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