Copper-catalyzed asymmetric C(sp)-H arylation for the synthesis of P- and axially chiral phosphorus compounds.

Transition metal-catalyzed C-H bond functionalization is an important method in organic synthesis, but the development of methods that are lower cost and have a less environmental impact is desirable. Here, a Cu-catalyzed asymmetric C(sp)-H arylation is reported. With diaryliodonium salts as arylating reagents, a range of ortho-arylated P-chiral phosphonic diamides were obtained in moderate to excellent yields with high enantioselectivities (up to 92% ee).

Palladium-Catalyzed Asymmetric Arylation of C(sp(3))-H Bonds of Aliphatic Amides: Controlling Enantioselectivity Using Chiral Phosphoric Amides/Acids.

Enantioselective arylation of secondary β-C(sp(3))-H bonds of 8-aminoquinoline amides was realized with a palladium catalyst. Chiral phosphoric amides and acids were used for the first time to control the stereoselectivity at the C-H bond cleavage step in the C-H activation reactions.

Palladium-catalyzed enantioselective C-H arylation for the synthesis of P-stereogenic compounds.

A palladium-catalyzed enantioselective C-H arylation of N-(o-bromoaryl)-diarylphosphinic amides is described for the synthesis of phosphorus compounds bearing a P-stereogenic center. The method provides good enantioselectivities and high yields. The products were readily transformed into P-chiral biphenyl monophosphine ligands.

2-Hydroxy-1,10-phenanthroline vs 1,10-phenanthroline: significant ligand acceleration effects in the palladium-catalyzed oxidative Heck reaction of arenes.

A series of bidentate monoanionic nitrogen ligands were designed and applied in the Pd-catalyzed oxidative Heck reaction of arenes with alkenes. Significant ligand-accelerated effects were observed, and direct C-H functionalized products were formed in high yields with meta-selectivity.