Allylic 1,3-rearrangement of thiophenyl substituted sulfones

✍ Scribed by Albert Padwa; William H. Bullock; Andrew D. Dyszlewski

• Publisher: Elsevier Science
• Year: 1987
• Tongue: French
• Weight: 230 KB
• Volume: 28
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)95469-8

✦ Synopsis

Substituted thiophenyl ally1 sulfones undergo a 1,3-allylic sulfonyl shift and this rearrangement has been utilized within a metallation-alkylation sequence.

The synthetic application of sulfones to the preparation of natural products has increased enormously during the past several years. 1~ This increased interest stems from the recognition that sulfones can stabilize anions,3,4 may be removed reductively5 and, where appropriate, may be eliminated to form olefins.6 Lately, there have been several reports in the literature which indicate that substituted allylic sulfones can undergo a 1,3-rearrangement.'-12

We have been involved in the preparation and utilization of ally1 sulfones of the general type 1, with the objective of performing metallation-alkylation, followed by 1,3-rearrangement, then a further metallationalkylation and finally hydrolysis of the vinyl sulfide.