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
Mild and Practical Indole C2 Allylation by Allylboration of in situ Generated 3-Chloroindolenines.
TL;DR: A selective C2 allylation strategy that proceeds via allylboration of in situ‐generated 3‐chloroindolenines is reported, which is mild, practical, and compatible with a wide range of C3‐substituted indoles.
(Pentamethylcyclopentadienyl)cobalt(III)‐Catalyzed C–H Bond Functionalization: From Discovery to Unique Reactivity and Selectivity
TL;DR: In this article, the unique reactivity and selectivity of Cp*Co(III) and the differences between the cobalt and rhodium catalysis are intensively discussed, due to the lower electronegativity, hard nature, and smaller ionic radius of cobalt.
Manganese(I)-Catalyzed Direct C-H Allylation of Arenes with Allenes.
TL;DR: A manganese(I)-catalyzed direct C-H coupling with allenes for the efficient assembly of allylated arenes offers an extremely high level of atom-economy and is particularly suited for the introduction of 1,1-disubstitiuted allyl groups, as exemplified by the quantitative syntheses of a variety of prenylated indoles.
Synthesis of Benzofulvenes via Cp*Co(III)-Catalyzed C-H Activation and Carbocyclization of Aromatic Ketones with Internal Alkynes.
TL;DR: A highly efficient and practical synthesis of benzofulvenes was developed via ketone-directed Cp*Co(III)-catalyzed sequential C-H activation, addition, cyclization, and dehydration cascade processes between simple aromatic ketones and alkynes.
References
The atom economy--a search for synthetic efficiency
TL;DR: Transition metal-catalyzed methods that are both selective and economical for formation of cyclic structures, of great interest for biological purposes, represent an important starting point for this long-term goal.
4.4K
Carboxylate-assisted transition-metal-catalyzed C-H bond functionalizations: mechanism and scope.
TL;DR: This review summarizes the development and scope of carboxylates as cocatalysts in transition-metal-catalyzed C-H functionalizations until autumn 2010 and proposes new acronyms, such as CMD (concerted metalationdeprotonation), IES (internal electrophilic substitution), or AMLA (ambiphilic metal ligand activation), which describe related mechanisms.
3.1K
C-H bond functionalization: emerging synthetic tools for natural products and pharmaceuticals
TL;DR: This Review provides an overview of C-H bond functionalization strategies for the rapid synthesis of biologically active compounds such as natural products and pharmaceutical targets.
2.7K
Weak coordination as a powerful means for developing broadly useful C-H functionalization reactions.
TL;DR: The motivation for studying Pd-catalyzed C-H functionalization assisted by weakly coordinating functional groups is discussed, and efforts to bring reactions of this type to fruition are chronicle.
2.5K