Iridium‐Catalyzed Ligand‐Controlled Remote para‐Selective C−H Activation and Borylation of Twisted Aromatic Amides

• Published in: Angewandte Chemie International Edition Vol. 61; no. 27; pp. e202203539 - n/a
• Main Authors: Hoque, Md Emdadul, Bisht, Ranjana, Unnikrishnan, Anju, Dey, Sayan, Mahamudul Hassan, Mirja Md, Guria, Saikat, Rai, Rama Nand, Sunoj, Raghavan B., Chattopadhyay, Buddhadeb
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 04.07.2022; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Amides; Borylation; Chemistry; Chemistry, Multidisciplinary; C−H Activation; Density Functional Calculations; Intermediates; Iridium; Iridium Catalyst; Ligands; Para Selectivity; Physical Sciences; Science & Technology; Selectivity; Substrates; Para Selectivity; REAGENTS; C-H Activation; ARENES; COMPLEXES; NONCOVALENT INTERACTIONS; Iridium Catalyst; FUNCTIONALIZATION; DISTORTION; Density Functional Calculations; CROSS-COUPLING REACTIONS; Borylation; DISTORTION/INTERACTION; C(SP)-H; DERIVATIVES; Keywords: C-H Activation Borylation para selectivity Iridium catalyst DFT calculation
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202203539

A method of para‐selective borylation of aromatic amides is described. The borylation proceeded via an unprecedented substrate–ligand distortion between the twisted aromatic amides and a newly designed ligand framework (defa) that is different from the traditionally used ligand (dtbpy) for the C−H borylation reactions. The designed ligand framework (defa) has led to the development of a new type of catalytic system that shows excellent para selectivity for a range of aromatic amides. Moreover, the designed ligand has shown excellent reactivity and selectivity for a range of heterocyclic aromatic amides. The identification of key transition states and intermediates using the DFT computations associated with the three regio‐isomeric pathways revealed that the most efficient catalytic pathway with the defa ligand leads to the para borylation while in the case of bpy the borylation at the para and meta sites compete. A highly para‐selective C−H borylation of aromatic amides is reported. The para borylation proceeds via an unprecedented substrate–ligand distortion between the twisted aromatic amides and a newly designed ligand framework (defa), which is different from the standard borylation ligand. A new type of catalytic system was developed by using this defa ligand that demonstrated excellent levels of para selectivity for a range of aromatic amides.