The zwitterion-accelerated [3,3]-sigmatropic rearrangement of allyl vinyl sulfoxided to sulfines. A specific class of charge-accelerated rearrangement
✍ Scribed by Jih Ru Hwu; Denise A Anderson
- Publisher
- Elsevier Science
- Year
- 1986
- Tongue
- French
- Weight
- 279 KB
- Volume
- 27
- Category
- Article
- ISSN
- 0040-4039
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✦ Synopsis
Conversion of aatyt Vinyl 8ulfOXide8 5 and 8 t0 y,b-UnSUtUZYZted S&fine8 8 and 9, respectively, under neutral condition8 8hOW8 that the acceterating effect8 of the charge8 in a awitterionic moiety do not cancel, instead the sulfoxide functionality significantly facilitates the rearrangement. Uncatalyzed [3,3]-sigmatropic rearrangement reactions can be accelerated by placing electron donating or withdrawing groups in the substrate, or more remarkably by introducing a positive or a negative charge into the system. Examples of cation-accelerated rearrangements include Breslow's carbocationic Cope rearrangement1 and the ammonium-iminium rearrangements.2 Anion-accelerated rearrangements include Ireland's ester enolate-Claisen rearrangement,3 Evans' anionic oxy-Cope rearrangement,4 and carbanionic Claisen rearrangements.5 Herein, we provide