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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.

DOI:10.1002/anie.202303345
PMID:37000412
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10213147/
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。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6354/10213147/fa54c187efaa/nihms-1888580-f0011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6354/10213147/4cf3d5c1e6e5/nihms-1888580-f0010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6354/10213147/fa54c187efaa/nihms-1888580-f0011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6354/10213147/4cf3d5c1e6e5/nihms-1888580-f0010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6354/10213147/fa54c187efaa/nihms-1888580-f0011.jpg

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