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. 2023 Oct 25;145(42):23160-23166.
doi: 10.1021/jacs.3c07436. Epub 2023 Oct 17.

Photoinduced Efficient Catalytic α-Alkylation Reactions of Active Methylene and Methine Compounds with Nonactivated Alkenes

Yasuhiro Yamashita  1 , Yoshihiro Ogasawara  1 , Trisha Banik  1 , Shu Kobayashi  1
Affiliations

Photoinduced Efficient Catalytic α-Alkylation Reactions of Active Methylene and Methine Compounds with Nonactivated Alkenes

Yasuhiro Yamashita et al. J Am Chem Soc. .

Abstract

In catalytic α-alkylation reactions of carbonyl compounds, although SN2-type substitution reactions of enolates with alkyl halides are a conventional methodology, addition reactions with alkenes are more desirable because of their atom-economical character; however, reactions with nonactivated alkenes are challenging. Here, we developed highly efficient catalytic α-alkylation reactions of active methylene and methine compounds with nonactivated alkenes such as 1-decene using an organophotocatalyst and lithium thiophenoxide as a Lewis acid/Brønsted base/hydrogen atom transfer (HAT) multifunctional catalyst under blue-light irradiation. The reaction was also performed with a higher degree of efficiency under a continuous-flow system to obtain the products in multigram scales. The present reaction system enables highly efficient and practical α-alkylation reactions of active methylene and methine compounds to be achieved.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Previous Examples and This Work
Scheme 2
Scheme 2. Application for Synthesis of Drug Molecules
Scheme 3
Scheme 3. Functionalization of Natural or Biologically Active Products
Figure 1
Figure 1
Proposed catalytic cycle.
See this image and copyright information in PMC

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References

    1. Comprehensive Organic Synthesis; Trost B. M.; Fleming I., Eds.; Pergamon, Vol. 3; 1991.
    1. Trost B. The Atom Economy-A Search for Synthetic Efficiency. Science 1991, 254, 1471–1477. 10.1126/science.1962206. - DOI - PubMed
    1. Dénès F.; Pérez-Luna A.; Chemla F. Addition of Metal Enolate Derivatives to Unactivated Carbon-Carbon Multiple Bonds. Chem. Rev. 2010, 110, 2366–2447. 10.1021/cr800420x. - DOI - PubMed
    1. Snider B. B. Manganese(III)-Based Oxidative Free-Radical Cyclization. Chem. Rev. 1996, 96, 339–363. 10.1021/cr950026m. - DOI - PubMed
    1. Wang X.; Widenhoefer R. A. Palladium(II)- and Platinum(II)-Catalyzed Addition of Stabilized Carbon Nucleophiles to Ethylene and Propylene. Chem. Commun. 2004, 660–661. 10.1039/b316734h. - DOI - PubMed