Aluminum-chloride catalyzed reaction of allylic sulfides with methyl propiolate: A novel addition reaction via an ionic [3.3] sigmatropic rearrangement

✍ Scribed by Kenji Hayakawa; Yoshimasa Kamikawaji; Ken Kanematsu

• Book ID: 104220790
• Publisher: Elsevier Science
• Year: 1982
• Tongue: French
• Weight: 226 KB
• Volume: 23
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)87291-3

✦ Synopsis

The aluminum-chloride catalyzed reaction of allyllc sulfides with methyl propiolate resulted ln the clean formatlon of novel 1 1 adducts via ionic [3 33 sigmatropic rearrangements. Pencyclic reactlons of organosulfur compounds have become increasingly important as a general synthetic method for the carbon-carbon bond formation.' Especially, allyllc sulfides are of great utility because of their ability to undergo a variety of rearrangements including the well-known name reactions such as the Stevens ([l 23) rearrangement,2 the Wlttlg ([l 21) rearrangement, 3 the Sotmnlet-Hauser ([2.3]) rearrangement,4 and the thlo-Clalsen ([3.3]) rearrangement. 5 Although ionic (or zwltterlonlc) species are often involved in these pericyclic reactions due to the unique properties of ~ulfur,~ no ionic [3 33 sigmatropic rearrangement of the organosulfur compounds 1s known We now report a novel Lewis-acid catalvzed addition reaction of allyllc sulfides to methvl proplolate (MP) via an ionic [3.3] sigmatropic rearrangement which 1s generally illustrated ln eq 1 (X=S) The idea originated ln our recent flndlnq (' \ =E R-x = . E(1) of the facile reaction of thebalne with MP ln polar solvents which could be regarded as the nitrogen case of eq 1 (X=NMe) ' Extension of this reaction to the organosulfur compounds would enhance Its synthetic utility because of the unusual versatlllty of vinyl sulfides to be formed