Enantioselective C-H bond functionalization under Co(III)-catalysis
Bholanath Garai1, Abir Das1, Doppalapudi Vineet Kumar1
1Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh - 208016, India. basker@iitk.ac.in.
Sustainable enantioselective C-H functionalization is advanced using earth-abundant cobalt catalysts. High-valent cobalt systems offer promising alternatives to precious metals for asymmetric catalysis.
Area of Science:
- Organic Chemistry
- Catalysis
- Sustainable Chemistry
Background:
- Precious 4d and 5d transition metal catalysts for enantioselective C-H functionalization face sustainability challenges due to resource depletion.
- Earth-abundant and low-toxicity 3d transition metals are emerging as sustainable alternatives.
- High-valent cobalt, particularly, shows unique reactivity for catalytic C-H functionalization.
Purpose of the Study:
- To review recent advancements in high-valent cobalt-catalyzed enantioselective C-H functionalization.
- To highlight the potential of cobalt as a sustainable catalyst in asymmetric synthesis.
- To encourage further research and discoveries in this evolving field.
Main Methods:
- Focus on high-valent cobalt catalysis for C-H functionalization.
- Exploration of cobalt catalysts with various chiral ligands and directing groups.
- Review of developments up to October 2023.
Main Results:
- Development of chiral Cp#Co(III)-catalysts.
- Utilization of chiral carboxylic acids with achiral Cp*Co(III)-catalysts.
- Investigation of cobalt/salox and cobalt/chiral phosphoric acid hybrid systems.
- Successful application in asymmetric catalysis with mono and bidentate directing groups.
Conclusions:
- High-valent cobalt catalysts are effective for enantioselective C-H functionalization.
- Cobalt offers a sustainable and viable alternative to precious metals in asymmetric catalysis.
- The field shows significant promise for future discoveries in synthetic chemistry.
Related Concept Videos
Regioselectivity of Electrophilic Additions-Peroxide Effect
Cycloaddition Reactions: MO Requirements for Photochemical Activation
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Benzene to 1,4-Cyclohexadiene: Birch Reduction Mechanism
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
Regioselectivity and Stereochemistry of Hydroboration
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...


