Journal Article10.1002/ANIE.201503704
Dehydrative Direct CH Allylation with Allylic Alcohols under [Cp*CoIII] Catalysis
Yudai Suzuki,Bo Sun,Ken Sakata,Tatsuhiko Yoshino,Tatsuhiko Yoshino,Shigeki Matsunaga,Shigeki Matsunaga,Motomu Kanai +7 more
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TL;DR: A cationic [Cp*Co(III)] catalyst promoted direct dehydrative C-H allylation with non-activated allyl alcohols, thus giving C2-allylated indoles, pyrrole, and phenyl-pyrazole in good yields, while analogous catalysts were not effective.
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Abstract: The unique reactivity of [Cp*CoIII] over [Cp*RhIII] was demonstrated. A cationic [Cp*CoIII] catalyst promoted direct dehydrative CH allylation with non-activated allyl alcohols, thus giving C2-allylated indoles, pyrrole, and phenyl-pyrazole in good yields, while analogous [Cp*RhIII] catalysts were not effective. The high γ-selectivity and C2-selectivity indicated that the reaction proceeded by directing-group-assisted CH metalation. DFT calculations suggested that the γ-selective substitution reaction proceeded by CH metalation and insertion of a CC double bond, with subsequent β-hydroxide elimination. The [Cp*CoIII] catalyst favored β-hydroxide elimination over β-hydride elimination.
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Citations
Mechanistic Exploration of Cp*CoIII/RhIII-Catalyzed Carboamination/Olefination of N-Phenoxyacetamides with Alkenes.
TL;DR: A computational study of Cp*CoIII/RhIII-catalyzed carboamination/olefination of N-phenoxyacetamides with alkenes was carried out to elucidate the catalyst-controlled chemoselectivity, uncovering that the higher propensity for the β-H-elimination of the C p*RhIII than the Cp-CoIII catalyst in the olefination pathway could be responsible for the different selectivity and reactivity of
Cobalt(III)-catalyzed efficient synthesis of indenones through carboannulation of benzoates and alkynes
TL;DR: In this paper, it was shown that the weak and simple ester directing group makes it an attractive protocol in carbocycle synthesis, and redox-neutral annulative coupling with internal alkynes allowed efficient synthesis of indenones.
Thioamide-Directed Cobalt(III)-Catalyzed Selective Amidation of C(sp3 )-H Bonds.
TL;DR: The reported method is a rare example of the use of a directing group other than the commonly used pyridine and quinolone classes for Cp*CoIII -catalyzed C(sp3 )-H functionalization and the first to exploit thioamides.
Thioamide-Directed Cp*Co(III)-Catalyzed C-H Allylation of Ferrocenes
TL;DR: In this article, the first Cp*Co(III)-catalyzed C-H allylation of ferrocene thioamides with allyl carbonates has been developed.
DFT analysis of the concerted metalation-deprotonation in earth-abundant 3d-transition-metal mediated C–H activations
William M. Grumbles,Cooper J. Kimbrough,Thomas R. Cundari +2 more
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