Department of Synthetic Chemistry and Biological Chemistry, Kyoto University, Katsura, Kyoto 615-8510, Japan.
J Am Chem Soc. 2012 Oct 24;134(42):17440-3. doi: 10.1021/ja308285r. Epub 2012 Oct 15.
Enaminones are synthesized by the rhodium(II)-catalyzed denitrogenative rearrangement reaction of 1-(N-sulfonyl-1,2,3-triazol-4-yl)alkanols, which are readily prepared from propargylic alcohols and N-sulfonyl azides. Intramolecular 1,2-hydride (or -alkyl) migration occurs with an intermediary α-imino rhodium(II) carbenoid species generated through denitrogenation of the 1,2,3-triazol-4-yl moiety. The resulting enaminones is converted into various heterocycles with replacement of the N-sulfonyl group.
烯胺酮是通过铑（II）催化的 1-（N-磺酰基-1,2,3-三唑-4-基）丙醇的脱氮重排反应合成的，该反应由炔丙醇和 N-磺酰基叠氮化物制备得到。分子内的 1,2-氢（或 -烷基）迁移发生在通过 1,2,3-三唑-4-基部分脱氮生成的中间体α-亚氨基铑（II）卡宾物种中。所得的烯胺酮可通过取代 N-磺酰基转化为各种杂环。
