Enantioselective Cobalt Catalysis: Precision Construction of C-N Atropisomers
Created on 08.15
A significant advancement in asymmetric catalysis has been achievedby Prof. Basker Sundararaju's team at IIT Kanpur. Their latest JACS publicationdemonstrates how Salox ligands enable unprecedented stereochemical control incobalt-catalyzed reactions.
Evolution of Salox Ligand TechnologySalox ligands, first reported by Prof. Carsten Bolm (1991), underwenttransformative development in 2022 when Prof. Shi Bingfeng's group pioneeredtheir application in "chirality-controlled catalytic C-Hfunctionalization". Key advantages include:
- Rigid scaffold with proximal chiral centers enabling precise stereodifferentiation
- Facile synthesis and derivatization potential
- Exceptional stability under catalytic conditions
Shi's subsequent research expanded Salox applications to diversestereochemical frameworks (central/planar/axial chirality) and novelelectrochemical/photochemical C-H activation systems (Acc. Chem. Res. 2025,58, 971).
Sundararaju Group's Methodology BreakthroughThe IIT Kanpur team has now leveraged Salox ligands for cobalt-catalyzedconstruction of C-N atropisomers featuring:
- Room-temperature operation with aerial oxygen as oxidant
- Atom-economic approach for sustainable synthesis
- Broad substrate tolerance across diverse aryl amides and alkynes
- Dual stereocontrol (enantio- and diastereoselectivity)
Key Stereochemical AdvantagesThe optimized Salox ligand system delivers:
- Exceptional enantiocontrol: >99% ee with (S)-L5 ligand
- Diastereodivergence: >20:1 dr with programmable stereochemistry
- Mechanistic versatility:
Publication DetailsThis study opens new possibilities in atroposelective synthesis:
- Title: Cobalt-Catalyzed Enantioselective and Diastereodivergent Construction of C-N Atropisomers
- Authors: Das, Kumaran, Maity, Premkumar & Sundararaju
- Journal: J. Am. Chem. Soc.
- DOI: 10.1021/jacs.5c03776