Synthesis of Enaminones by Rhodium-Catalyzed Denitrogenative Rearrangement of 1‑(N‑Sulfonyl-1,2,3-triazol-4-yl)alkanols

• Published in: Journal of the American Chemical Society Vol. 134; no. 42; pp. 17440 - 17443
• Main Authors: Miura, Tomoya, Funakoshi, Yuuta, Morimoto, Masao, Biyajima, Tsuneaki, Murakami, Masahiro
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 24-10-2012
• Subjects: Alcohols - chemistry; Amines - chemical synthesis; Amines - chemistry; Catalysis; Molecular Structure; Organometallic Compounds - chemistry; Rhodium - chemistry
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja308285r

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.