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O-Benzyl Xanthate Esters under Ni/Photoredox Dual Catalysis: Selective Radical Generation and Csp3-Csp2 Cross-Coupling.

ABSTRACT: Alkyl xanthate esters are perhaps best known for their use in deoxygenation chemistry. However, their use in cross-coupling chemistry has not been productive, which is due, in part, to inadequate xanthate activation strategies. Herein, we report the use of O-benzyl xanthate esters, readily derived from alcohols, as radical pronucleophiles in Csp3-Csp2 cross-couplings under Ni/photoredox dual catalysis. Xanthate (C-O) cleavage is found to be reliant on photogenerated (sec-butyl) radical activators to form new carbon-centered radicals primed for nickel-catalyzed cross-couplings. Mechanistic experiments support the fact that the key radical components are formed independently, and relative rates are carefully orchestrated, such that no cross reactivity is observed.

SUBMITTER: Vara BA

PROVIDER: S-EPMC5460664 | biostudies-literature | 2017 Jun

REPOSITORIES: biostudies-literature

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O-Benzyl Xanthate Esters under Ni/Photoredox Dual Catalysis: Selective Radical Generation and Csp3-Csp2 Cross-Coupling.

Vara Brandon A BA Patel Niki R NR Molander Gary A GA

ACS catalysis 20170509 6

Alkyl xanthate esters are perhaps best known for their use in deoxygenation chemistry. However, their use in cross-coupling chemistry has not been productive, which is due, in part, to inadequate xanthate activation strategies. Herein, we report the use of O-benzyl xanthate esters, readily derived from alcohols, as radical pronucleophiles in Csp3-Csp2 cross-couplings under Ni/photoredox dual catalysis. Xanthate (C-O) cleavage is found to be reliant on photogenerated ...[more]

PMID: 28603657

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