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Copper‐Catalyzed Extended Pummerer Reactions of Ketene Dithioacetal Monoxides with Alkynyl Sulfides and Ynamides with an Accompanying Oxygen Rearrangement |
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| Authors: | Dr Kei Murakami Junichi Imoto Prof Dr Hiroshi Matsubara Dr Suguru Yoshida Prof Dr Hideki Yorimitsu Prof Dr Koichiro Oshima |
| Institution: | 1. Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto‐daigaku Katsura, Nishikyo‐ku, Kyoto 615‐8510 (Japan), Fax: (+81)?75‐753‐7710;2. Department of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa, Sakyo‐ku, Kyoto 606‐8502 (Japan), Fax: (+81)?75‐753‐3970;3. Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Gakuen‐cho 1‐1, Naka‐ku, Sakai 599‐8531 (Japan), Fax: (+81)?72‐252‐1161;4. ACT‐C, Japan Science and Technology Agency (Japan);5. Environment, Safety and Health Organization, Kyoto University, Yoshida‐honmachi, Sakyo‐ku, Kyoto, 606‐8501 (Japan) |
| Abstract: | The first examples of metal‐catalyzed extended Pummerer reactions through the activation of sulfoxides are described. The copper‐catalyzed reactions of ketene dithioacetal monoxides with alkynyl sulfides and ynamides provided a wide variety of γ,γ‐disulfanyl‐β,γ‐unsaturated carbonyl compounds with an accompanying oxygen rearrangement. The products can be easily converted into 1,4‐dicarbonyl compounds and substituted heteroaromatics. DFT calculations and mechanistic experiments revealed a new interesting stepwise addition/oxygen rearrangement mechanism. |
| Keywords: | alkynes copper Pummerer reactions rearrangement sulfur heterocycles |