Lewis Acid–Base Interaction‐Controlled ortho‐Selective C−H Borylation of Aryl Sulfides

• Published in: Angewandte Chemie International Edition Vol. 56; no. 6; pp. 1495 - 1499
• Main Authors: Li, Hong Liang, Kuninobu, Yoichiro, Kanai, Motomu
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 01.02.2017; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Aromatic compounds; Biocompatibility; borylation; Catalysis; Chemical synthesis; Chemistry; Chemistry, Multidisciplinary; C−H activation; Iridium; Lewis acid; Lewis acid–base interactions; Ligands; noncovalent bonding; ortho-selectivity; Physical Sciences; Science & Technology; Selectivity; Sulfides; Sulfur; Lewis acid-base interactions; CUPRIC ACETATE; ortho-selectivity; ROOM-TEMPERATURE; borylation; ARENES; COMPLEXES; ARYLBORONIC ACIDS; noncovalent bonding; CROSS-COUPLING REACTIONS; C-H activation; PHENOLS; CATALYZED BORYLATION; DIARYL ETHERS; DERIVATIVES; C−H activation
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201610041

An iridium/bipyridine‐catalyzed ortho‐selective C−H borylation of aryl sulfides was developed. High ortho‐selectivity was achieved by a Lewis acid–base interaction between a boryl group of the ligand and a sulfur atom of the substrate. This is the first example of a catalytic and regioselective C−H transformation controlled by a Lewis acid–base interaction between a ligand and a substrate. The C−H borylation reaction could be conducted on a gram scale, and with a bioactive molecule as a substrate, demonstrating its applicability to late‐stage regioselective C−H borylation. A bioactive molecule was synthesized from an ortho‐borylated product by converting the boryl and methylthio groups of the product. An iridium/bipyridine‐catalyzed ortho‐selective C−H borylation of aryl sulfides has been developed. High ortho‐selectivity was achieved by a Lewis acid–base interaction between a ligand boryl group and a substrate sulfur atom. This is the first example of a catalytic and regioselective C−H transformation controlled by a Lewis acid–base interaction between ligand and substrate.