Photo-Induced Pyridylic\nC(sp<sup>3</sup>)–H\nAlkylation with Unactivated Alkenes Enabled by Hydrogen Atom Transfer/Lewis\nAcid Cocatalysis

Radical\nhydroalkylation of alkenes represents an ideal\napproach\nfor C(sp<sup>3</sup>)–C(sp<sup>3</sup>) bond formation. However,\nradical precursors have been substantially limited due to the sluggish\nnature of less electrophilic carbon-centered radicals to participate\nin addition step toward unactivated alkenes. Herein, we demonstrate\nthat this inherent limitation can be overcome by the use of a Lewis\nacid catalyst. This cocatalytic system enables the hitherto elusive\nradical C(sp<sup>3</sup>)–C(sp<sup>3</sup>) bond formation\nbetween pyridylacetates and unactivated alkenes to generate medically\nrelevant valuable products. Computational studies support that the\nformation of a Lewis pair with the substrates is crucial to lower\nthe energy of the transition state for the rate-determining radical\naddition step.

Publication Details

Journal
Figshare
Published
2024-09-27
DOI
https://doi.org/10.1021/acscatal.4c05026.s001
Primary Topic
Wheat and Barley Genetics and Pathology
Type
article
Field-Weighted Citation Impact
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article

Photo-Induced Pyridylic\nC(sp3)–H\nAlkylation with Unactivated Alkenes Enabled by Hydrogen Atom Transfer/Lewis\nAcid Cocatalysis

Figshare
Wheat and Barley Genetics and Pathology
article

Photo-Induced Pyridylic\nC(sp3)–H\nAlkylation with Unactivated Alkenes Enabled by Hydrogen Atom Transfer/Lewis\nAcid Cocatalysis

article en

Abstract

Radical\nhydroalkylation of alkenes represents an ideal\napproach\nfor C(sp<sup>3</sup>)–C(sp<sup>3</sup>) bond formation. However,\nradical precursors have been substantially limited due to the sluggish\nnature of less electrophilic carbon-centered radicals to participate\nin addition step toward unactivated alkenes. Herein, we demonstrate\nthat this inherent limitation can be overcome by the use of a Lewis\nacid catalyst. This cocatalytic system enables the hitherto elusive\nradical C(sp<sup>3</sup>)–C(sp<sup>3</sup>) bond formation\nbetween pyridylacetates and unactivated alkenes to generate medically\nrelevant valuable products. Computational studies support that the\nformation of a Lewis pair with the substrates is crucial to lower\nthe energy of the transition state for the rate-determining radical\naddition step.

Figshare
Openalex Percentile: Top 40%
Wheat and Barley Genetics and Pathology
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