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. 2018 May 2;140(17):5701-5705.
doi: 10.1021/jacs.8b02834. Epub 2018 Apr 20.

Decarboxylative Hydroalkylation of Alkynes

Nicholas A Till  1 , Russell T Smith  1 , David W C MacMillan  1
Affiliations

Decarboxylative Hydroalkylation of Alkynes

Nicholas A Till et al. J Am Chem Soc. .

Abstract

The merger of open- and closed-shell elementary organometallic steps has enabled the selective intermolecular addition of nucleophilic radicals to unactivated alkynes. A range of carboxylic acids can be subjected to a CO2 extrusion, nickel capture, migratory insertion sequence with terminal and internal alkynes to generate stereodefined functionalized olefins. This platform has been further extended, via hydrogen atom transfer, to the direct vinylation of unactivated C-H bonds. Preliminary studies indicate that a Ni-alkyl migratory insertion is operative.

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Conflict of interest statement

Notes

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Dual-catalytic alkyne hydroalkylation.
Scheme 1
Scheme 1
Proposed Dual-Catalytic Cycle
Scheme 2
Scheme 2
Alkylation Selectivity as a Function of Acid Size
See this image and copyright information in PMC

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