Iridium-Catalyzed Preparation of Silylboranes by Silane Borylation and Their Use in the Catalytic Borylation of Arenes

• Published in: Organometallics Vol. 27; no. 22; pp. 6013 - 6019
• Main Authors: Boebel, Timothy A, Hartwig, John F
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 24.11.2008; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Physical Sciences; Science & Technology; ROOM-TEMPERATURE; PALLADIUM; ASYMMETRIC SILABORATION; REGIOSELECTIVE SILABORATION; COMPLEXES; BONDS; TERMINAL ALKYNES; REGIOSPECIFIC FUNCTIONALIZATION; PINACOLBORANE; C-H BORYLATION
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om800696d

Silylboranes are versatile reagents for transition metal-catalyzed reactions of unsaturated organic molecules. These reagents are typically prepared by the addition of a silyl lithium species to a boron electrophile. However, the need to generate anionic silane reagents limits the scope of silylboranes that can be readily obtained. Here, we describe the synthesis of trialkylsilylboranes by the borylation of silanes catalyzed by iridium complexes. The reaction of trialkylhydrosilanes with B2pin2 catalyzed by the combination of [Ir(OMe)cod]2 and 4,4′-di-tert-butylbipyridine forms trialkylsilylboronic esters. In addition, we show that these trialkylsilylboranes serve as boron sources for the iridium-catalyzed borylation of aryl C−H bonds. In contrast to diboron reagents, the silylboranes react with methylarenes at both the aryl and methyl C−H bonds.