Selective CH Borylation of Alkenes by Palladium Pincer Complex Catalyzed Oxidative Functionalization

Abstract

Die C‐H‐Borylierung einfacher Alkene gelang mit dem Palladium‐Pinzettenkomplex 1 als Katalysator in Gegenwart von hypervalentem Iod und Bis(pinacolato)dibor(B2pin2)‐Verbindungen. Die Borylierung verläuft vermutlich über eine Folge aus PdII→PdIV‐Oxidation und Diboronat‐Transmetallierung. TFA=Trifluoracetat

Ligand‐Promoted Borylation of C(sp3)H Bonds with Palladium(II) Catalysts

“…[6] In contrast, the development of CÀHb orylation reactions with Pd catalysts has met with limited success. [7] Building on the Pd II -catalyzed cross-coupling of C À Hb onds with organoboron reagents, [8] we and others developed rare examples of directed ortho borylation reactions of arenes with Pd catalysts (Scheme 1a). [9] Recently,Daugulis bidentate directing group has been applied to the C(sp 3 )ÀHb orylation of amines with 20 mol %o faP dc atalyst (Scheme 1b), but this method was limited to methyl C À Hb onds.…”

Low symmetry Pincer Ligands designed for applications in coordination chemistry and catalysis

“…Allylic substitution reactions catalyzed by palladium complexes have become an important set of transformations in modern organic chemistry. [77][78][79][80][81] The first series of reports on allylation of aldehydes and imines catalyzed by bis(allyl)palladium species was published by Yamamoto and coworkers in 1996, where the allyltributyltin was the source of the allyl group. 82 However, there are two inherent drawbacks with using bis(allyl) complexes.…”

Ligand‐Enabled δ‐C(sp3)−H Borylation of Aliphatic Amines

“…[14] In contrast, very limited success has been obtained in palladium catalysis. [15] These approaches were dedicated towards achieving direct borylation selectively and precisely at as pecific position in ac omplex molecule. Although numerous reports are available in the literature about the directed ortho C-H borylation reactions of arenes with Pd catalysis, [16] methodologies for direct borylation of inert C(sp 3 )ÀHb onds in an aliphatic chain is scarce.A mong those,o nly af ew palladium catalyzed distal C(sp 3 )-H borylation strategies can be found.…”