钌催化的末端炔烃与伯醇或醛的 C-C 偶联：通过氧化炔基化生成α,β-乙炔基酮（Ynones）。
Ruthenium-Catalyzed C-C Coupling of Terminal Alkynes with Primary Alcohols or Aldehydes: α,β-Acetylenic Ketones (Ynones) via Oxidative Alkynylation.
机构信息
University of Texas at Austin, Department of Chemistry, 105 E 24th St. (A5300), Austin, TX 78712-1167, USA.
出版信息
Angew Chem Int Ed Engl. 2023 Jun 5;62(23):e202303345. doi: 10.1002/anie.202303345. Epub 2023 Apr 26.
Abstract
The first metal-catalyzed oxidative alkynylations of primary alcohols or aldehydes to form α,β-acetylenic ketones (ynones) are described. Deuterium labelling studies corroborate a novel reaction mechanism in which alkyne hydroruthenation forms a transient vinylruthenium complex that deprotonates the terminal alkyne to form the active alkynylruthenium nucleophile.
摘要
首次报道了金属催化的伯醇或醛的氧化炔基化反应，生成α,β-乙酰基酮（炔酮）。氘标记研究证实了一种新的反应机理，其中炔烃的水合钌化形成瞬态的乙烯基钌络合物，该络合物使末端炔烃去质子化，形成活性炔基钌亲核试剂。
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