Propargyl sulphenates, rearrangement

Polychloromethylsulphonylbiphenyls, mass spectra of 154, 155 Polyenes, synthesis of 771 Polymerization, of sulphoxides 846 Polymer-supported reagents 928 Polymorphonuclear leukocytes 854 Poly(olefin sulphonejs, radiolysis of 916-922 Polysulphones, radiolysis of 913 Population analysis 14, 15, 21, 22 Propargylic sulphenates, rearrangement of 736-739... 

Rearrangement of acetylenic sulphenates to the allenic sulphoxides 151 was discovered when the synthesis of propargylic ester of trichloromethanesulphenic acid 152 was attempted (equation 86). This reaction is of general scope and gives very good yields of allenic sulphoxides (Table 14) from structurally diverse cohols and various sulphenyl chlorides Reaction of alkynols 153 with benzenesulphenyl chloride in the presence... 

In contrast, the reverse of the sulphoxide-sulphenate ester rearrangement forms the basis for the synthesis of the dienes (261) and (262) and the enamine (263). The diene (261) is obtained via two consecutive 2,3-sigmatropic rearrangements when the butynediol (264 X = H) is treated with PhSCl-NEta, whereas diene (262) is formed after one 2,3-rearrangement from the mono-acetylated butynediol (264 X = Ac). When the same reagent combination is used with the propargyl alcohols (265) a similar 2,3-rearrangement occurs and... 

---