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DOI: 10.1055/a-1914-7261
Recent Advances in the Generation of Onium Ylides for Sommelet–Hauser Rearrangements
Our studies were supported by JSPS KAKENHI (Grant Numbers 23750037, 19750029, and 17750034), the Mitsubishi Chemical Corporation Foundation, the Asahi Glass Foundation, the Union Tool Scholarship Foundation, the Foundation for Japanese Chemical Research, and the Uchida Energy Science Promotion Foundation.
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Abstract
The Sommelet–Hauser rearrangement of X-benzylic onium ylides (X = heteroatom) is an interesting transformation in organic synthesis. This rearrangement proceeds via dearomative [2,3]-sigmatropic rearrangement, followed by aromatization to form a carbon(sp2)–carbon(sp3) bond. Few advances were made in studies performed around 2000 on this rearrangement because of several competitive side reactions and structural limitations. However, studies performed in the last 15 years on the rearrangement have remarkably expanded the substrate scope and synthetic applications. In this review, the utility of the Sommelet–Hauser rearrangement and recent advances for the generation of onium ylides are described.
1 Introduction
2 Base-Induced Rearrangement
3 Transition-Metal-Catalyzed Rearrangement
4 Light-Mediated Rearrangement
5 Aryne-Induced Rearrangement
6 Conclusions and Outlook
Key words
rearrangements - Sommelet–Hauser - sigmatropic - dearomative [2,3] - onium ylides - onium saltsPublication History
Received: 07 July 2022
Accepted after revision: 01 August 2022
Accepted Manuscript online:
01 August 2022
Article published online:
29 August 2022
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For a review on the Sommelet–Hauser (S–H) rearrangement:
For representative reviews on onium ylide rearrangements taken up the S–H rearrangement:
Theoretical studies:
In a previous review (ref. 2i), Ingold and Jessop’s study on the sulfonium ylide in 1930 was presented as the first example of the S–H rearrangement. Hughes and Kuriyan later reported a similar result in 1935. However, no product assignments were made in these reports. The assignments were made by Hilbert and Pinck in 1938. See:
Representative studies:
Examples of base-induced S–H rearrangement of ammonium salts apart from Hauser and co-workers before 2007:
Examples of base-induced S–H rearrangement of sulfonium salts:
Examples of base-induced S–H rearrangement of in situ generated azasulfonium salts:
Representative initial studies: