Iridium‐Catalyzed Formyl‐Selective Deuteration of Aldehydes

• Published in: Angewandte Chemie International Edition Vol. 56; no. 27; pp. 7808 - 7812
• Main Authors: Kerr, William J., Reid, Marc, Tuttle, Tell
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 26.06.2017; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Aldehydes; Catalysts; Chemistry; Chemistry, Multidisciplinary; Computer applications; C−H activation; Deuteration; Deuterium; DFT; Iridium; Labeling; Marking; Physical Sciences; Science & Technology; deuteration; ALKENE; H/D EXCHANGE; MECHANISM; DEHYDROGENATIVE DECARBONYLATION; COMPLEXES; PRIMARY ALCOHOLS; DEUTERIUM; iridium; aldehydes; C-H activation; DFT; HYDROGEN-ISOTOPE-EXCHANGE; BOND ACTIVATION; C−H activation
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201702997

We report the first direct catalytic method for formyl‐selective deuterium labeling of aromatic aldehydes under mild conditions, using an iridium‐based catalyst designed to favor formyl over aromatic C−H activation. A good range of aromatic aldehydes is selectively labeled, and a one‐pot labeling/olefination method is also described. Computational studies support kinetic product control over competing aromatic labeling and decarbonylation pathways. Al(D)hydes: An iridium catalyst system was designed to effect formyl over aryl C−H activation of aromatic aldehydes. Computational studies support kinetic product control over competing aromatic labeling and decarbonylation pathways.