Photoinduced 1,2-Hydro(cyanomethylation) of Alkenes with a Cyanomethylphosphonium Ylide

An efficient method has been developed for the 1, 2-hydro(cyanomethylation) of alkenes, in which a cyanomethyl radical species is generated from a cyanomethylphosphonium ylide by irradiation with visible light in the presence of an iridium complex, a thiol, and ascorbic acid. The cyanomethyl radical species then adds across the C=C double bond of an alkene to form an elongated alkyl radical species that accepts a hydrogen atom from the thiol to produce an elongated aliphatic nitrile. The ascorbic acid acts as the reductant to complete the catalytic cycle

N-スルホニル-l, 2, 3- トリアゾールを経由する末端アルキンとスルホニルアジドからの含窒素化合物の合成法

京都大学0048新制・課程博士博士(工学)甲第20713号工博第4410号新制||工||1685(附属図書館)京都大学大学院工学研究科合成・生物科学専攻(主査)教授 村上 正浩, 教授 杉野目 道紀, 教授 松原 誠二郎学位規則第4条第1項該当Doctor of Philosophy (Engineering)Kyoto UniversityDFA

Synthesis of Penta-2,4-dien-1-imines and 1,2-Dihydropyridines by Rhodium-Catalyzed Reaction of <i>N</i>‑Sulfonyl-1,2,3-triazoles with 2‑(Siloxy)furans

A rhodium­(II)-catalyzed reaction of <i>N</i>-sulfonyl-1,2,3-triazoles with 2-(siloxy)­furans is reported. Either open-chain penta-2,4-dien-1-imines or cyclic 1,2-dihydropyridines are selectively obtained depending on the ligand on rhodium­(II)

Intramolecular Dearomatizing [3 + 2] Annulation of α‑Imino Carbenoids with Aryl Rings Furnishing 3,4-Fused Indole Skeletons

The rhodium-catalyzed dearomatizing [3 + 2] annulation reaction of 4-(3-arylpropyl)-1,2,3-triazoles is described. It provides a straightforward synthetic pathway from simple 5-aryl-1-alkynes leading to tricyclic 3,4-fused dihydroindoles via the corresponding 1,2,3-triazoles

Direct Production of Enaminones from Terminal Alkynes via Rhodium-Catalyzed Reaction of Formamides with <i>N</i>‑Sulfonyl-1,2,3-triazoles

A rhodium-catalyzed reaction of formamides with <i>N</i>-sulfonyl-1,2,3-triazoles is developed to formulate a new one-pot procedure for the direct synthesis of α-amino enaminones from terminal alkynes

Direct Production of Enaminones from Terminal Alkynes via Rhodium-Catalyzed Reaction of Formamides with <i>N</i>‑Sulfonyl-1,2,3-triazoles

A rhodium-catalyzed reaction of formamides with <i>N</i>-sulfonyl-1,2,3-triazoles is developed to formulate a new one-pot procedure for the direct synthesis of α-amino enaminones from terminal alkynes

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

Enaminones are synthesized by the rhodium­(II)-catalyzed denitrogenative rearrangement reaction of 1-(<i>N</i>-sulfonyl-1,2,3-triazol-4-yl)­alkanols, which are readily prepared from propargylic alcohols and <i>N</i>-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 <i>N</i>-sulfonyl group

Facile Synthesis of 2,5-Disubstituted Thiazoles from Terminal Alkynes, Sulfonyl Azides, and Thionoesters

A sequential procedure for the synthesis of 2,5-disubstituted thiazoles from terminal alkynes, sulfonyl azides, and thionoesters is reported. A copper­(I)-catalyzed 1,3-dipolar cycloaddition of terminal alkynes with sulfonyl azides affords 1-sulfonyl-1,2,3-triazoles, which then react with thionoesters in the presence of a rhodium­(II) catalyst. The resulting 3-sulfonyl-4-thiazolines subsequently aromatize into the corresponding 2,5-disubstituted thiazoles by elimination of the sulfonyl group