Copper-catalysed photoinduced decarboxylative alkynylation: a combined experimental and computational study

Redox-active esters (RAEs) as alkyl radical precursors have demonstrated great advantages for C-C bond formation. A decarboxylative cross-coupling method is described to afford substituted alkynes from various carboxylic acids using copper catalysts CuCl and Cu(acac) 2 . The photoexcitation of coppe...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2020-05, Vol.11 (19), p.4939-4947
Main Authors: Mao, Yu, Zhao, Wenxuan, Lu, Shuo, Yu, Lei, Wang, Yi, Liang, Yong, Ni, Shengyang, Pan, Yi
Format: Article
Language:English
Subjects:
Aliphatic compounds
Alkynes
Carboxylic acids
Chemical engineering
Chemical reactions
Chemistry
Copper
Covalent bonds
Cross coupling
Esters
Ligands
Photoexcitation
Silanes
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Summary:Redox-active esters (RAEs) as alkyl radical precursors have demonstrated great advantages for C-C bond formation. A decarboxylative cross-coupling method is described to afford substituted alkynes from various carboxylic acids using copper catalysts CuCl and Cu(acac) 2 . The photoexcitation of copper acetylides with electron-rich NEt 3 as a ligand provides a general strategy to generate a range of alkyl radicals from RAEs of carboxylic acids, which can be readily coupled with a variety of aromatic alkynes. The scope of this cross-coupling reaction can be further expanded to aliphatic alkynes and alkynyl silanes using a catalytic amount of preformed copper-phenylacetylide. In addition, DFT calculations revealed the favorable reaction pathway and that the bidentate acetylacetonate ligand of the copper intermediate plays an important role in inhibiting the homo-coupling of the alkyne. Redox-active esters (RAEs) as alkyl radical precursors have demonstrated great advantages for Cu-catalysed C-C bond formation.
ISSN:2041-6520
2041-6539
DOI:10.1039/d0sc02213f