Palladium‐Catalyzed Carbon–Fluorine and Carbon–Hydrogen Bond Alumination of Fluoroarenes and Heteroarenes

• Published in: Angewandte Chemie International Edition Vol. 56; no. 41; pp. 12687 - 12691
• Main Authors: Chen, Wenyi, Hooper, Thomas N., Ng, Jamues, White, Andrew J. P., Crimmin, Mark R.
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 02.10.2017; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: alumination; Carbon; Catalysis; Chemistry; Chemistry, Multidisciplinary; C−F activation; C−H activation; Fluorine; fluoroarenes; hydrodefluorination; Hydrogen bonds; Palladium; Phosphine; Physical Sciences; Science & Technology; Selectivity; RHODIUM; hydrodefluorination; BUILDING-BLOCKS; OXIDATIVE ADDITION; CLEAVAGE; fluoroarenes; MEDICINAL CHEMISTRY; FUNCTIONALIZATION; C-H activation; C(SP)-F BONDS; alumination; C-F activation; BORYLATION; C−H activation; C−F activation
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201706378

Through serendipitous discovery, a palladium bis(phosphine) complex was identified as a catalyst for the selective transformation of sp2C−F and sp2C−H bonds of fluoroarenes and heteroarenes to sp2C−Al bonds (19 examples, 1 mol % Pd loading). The carbon–fluorine bond functionalization reaction is highly selective for the formation of organoaluminium products in preference to hydrodefluorination products (selectivity=4.4:1 to 27:1). Evidence is presented for a tandem catalytic process in which hydrodefluorination is followed by sp2C−H alumination. The taming of the fluorine: A palladium catalyst was identified for the transformation of C−F and C−H bonds of fluoroarenes and heteroarenes into sp2C−Al bonds. The carbon–fluorine bond functionalization reaction is highly selective for the formation of organoaluminium products in preference to hydrodefluorination products.