Sterically Controlled Lewis Acid−Base Interaction Toward para-Selective Borylation of Aromatic Aldimines and Benzylamines
Saikat Guria
Department of Biological & Synthetic Chemistry, Center of Biomedical Research, SGPGIMS Campus, Raebareli Road, Lucknow, 226014 Uttar Pradesh, India
Search for more papers by this authorDr. Mirja Md Mahamudul Hassan
Department of Biological & Synthetic Chemistry, Center of Biomedical Research, SGPGIMS Campus, Raebareli Road, Lucknow, 226014 Uttar Pradesh, India
Search for more papers by this authorSayan Dey
Department of Biological & Synthetic Chemistry, Center of Biomedical Research, SGPGIMS Campus, Raebareli Road, Lucknow, 226014 Uttar Pradesh, India
Search for more papers by this authorProf. Dr. Krishna Nand Singh
Department of Chemistry, Institute of Science, Banaras Hindu University, Varanasi, 221005 India
Search for more papers by this authorCorresponding Author
Dr. Buddhadeb Chattopadhyay
Department of Biological & Synthetic Chemistry, Center of Biomedical Research, SGPGIMS Campus, Raebareli Road, Lucknow, 226014 Uttar Pradesh, India
Search for more papers by this authorSaikat Guria
Department of Biological & Synthetic Chemistry, Center of Biomedical Research, SGPGIMS Campus, Raebareli Road, Lucknow, 226014 Uttar Pradesh, India
Search for more papers by this authorDr. Mirja Md Mahamudul Hassan
Department of Biological & Synthetic Chemistry, Center of Biomedical Research, SGPGIMS Campus, Raebareli Road, Lucknow, 226014 Uttar Pradesh, India
Search for more papers by this authorSayan Dey
Department of Biological & Synthetic Chemistry, Center of Biomedical Research, SGPGIMS Campus, Raebareli Road, Lucknow, 226014 Uttar Pradesh, India
Search for more papers by this authorProf. Dr. Krishna Nand Singh
Department of Chemistry, Institute of Science, Banaras Hindu University, Varanasi, 221005 India
Search for more papers by this authorCorresponding Author
Dr. Buddhadeb Chattopadhyay
Department of Biological & Synthetic Chemistry, Center of Biomedical Research, SGPGIMS Campus, Raebareli Road, Lucknow, 226014 Uttar Pradesh, India
Search for more papers by this authorAbstract
Site-selective C−H bond functionalization of arenes at the para position remains extremely challenging primarily due to its relative inaccessibility from the catalytic site. As a consequence, it is significantly restricted to limited molecular scaffolds. Herein, we report a method for the para-C−H borylation of aromatic aldimines and benzylamines using commercially available ligands under iridium catalysis. The established method displays excellent para selectivity for variously substituted aromatic aldimines, benzylamines and bioactive molecules. Based on several control experiments, it is proposed that a Lewis acid−base interaction between the nitrogen and boron functionality guides the para selectivity via a steric shield for the aromatic aldimines, where Bpin acts as a transient directing group. However, the steric shield of the in situ generated N−Bpin moiety controlled the overall selectivity for the para borylation of benzylamines.
Conflict of Interests
The authors declare no conflict of interest.
Open Research
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