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Generation of Dithianyl and Dioxolanyl Radicals Using Photoredox Catalysis: Application in the Total Synthesis of the Danshenspiroketallactones via Radical Relay Chemistry.

ABSTRACT: Visible-light-induced generation of dithianyl and dioxolanyl radicals via selective hydrogen atom transfer (HAT) has been achieved. This radical relay tactic enables remote C(sp3)-H functionalization to permit rapid access to polyol and spiroketal segments, and in turn has been exploited as a key synthetic construct in the total synthesis of the danshenspiroketallactones. The conformational stability of the danshenspiroketallactones has also been defined via experiments and DFT calculations.

SUBMITTER: Deng Y

PROVIDER: S-EPMC6518407 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature

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Generation of Dithianyl and Dioxolanyl Radicals Using Photoredox Catalysis: Application in the Total Synthesis of the Danshenspiroketallactones via Radical Relay Chemistry.

Deng Yifan Y Nguyen Minh D MD Zou Yike Y Houk K N KN Smith Amos B AB

Organic letters 20190226 6

Visible-light-induced generation of dithianyl and dioxolanyl radicals via selective hydrogen atom transfer (HAT) has been achieved. This radical relay tactic enables remote C(sp<sup>3</sup>)-H functionalization to permit rapid access to polyol and spiroketal segments, and in turn has been exploited as a key synthetic construct in the total synthesis of the danshenspiroketallactones. The conformational stability of the danshenspiroketallactones has also been defined via experiments and DFT calcul ...[more]

PMID: 30807194

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