C(sp3) Cross-Couplings of Benzyl and Tertiary Halides with Thiols or Alcohols Catalyzed by Iron DOI Creative Commons
Julius Semenya,

Yuan-Jie Yang,

Kimberly A. Giannantonio

et al.

Published: June 19, 2024

Various metal catalysts have proven effective in carbon–heteroatom bond formation with softer heteroatomic nucleophiles, but examples remain largely limited to sp2 hybridized carbon electrophiles. Here, we report the coupling of sp3 benzyl or tertiary halides soft thiol nucleophiles catalyzed by iron. The reaction is broad substrate scope for both partners and applicable construction congested tri- tetrasubstituted carbon-centers as well beta-quaternary thioethers. synthetic utility further emphasized alcohol gram-scale synthesis, bioconjugation, rapid herbicide library synthesis. Results from mechanistic experiments are consistent a stereoablative pathway that likely involves radical intermediate. Overall, provide an efficient method prepare pharmaceutically materially relevant carbon–sulfur carbon–oxygen bonds expanding iron-catalyzed cross-coupling reactions electrophiles nucleophiles.

Language: Английский

C(sp3) Cross-Couplings of Benzyl and Tertiary Halides with Thiols or Alcohols Catalyzed by Iron DOI Creative Commons
Julius Semenya,

Yuan-Jie Yang,

Kimberly A. Giannantonio

et al.

Published: June 19, 2024

Various metal catalysts have proven effective in carbon–heteroatom bond formation with softer heteroatomic nucleophiles, but examples remain largely limited to sp2 hybridized carbon electrophiles. Here, we report the coupling of sp3 benzyl or tertiary halides soft thiol nucleophiles catalyzed by iron. The reaction is broad substrate scope for both partners and applicable construction congested tri- tetrasubstituted carbon-centers as well beta-quaternary thioethers. synthetic utility further emphasized alcohol gram-scale synthesis, bioconjugation, rapid herbicide library synthesis. Results from mechanistic experiments are consistent a stereoablative pathway that likely involves radical intermediate. Overall, provide an efficient method prepare pharmaceutically materially relevant carbon–sulfur carbon–oxygen bonds expanding iron-catalyzed cross-coupling reactions electrophiles nucleophiles.

Language: Английский

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