Qingjing Yang

Copper-Catalyzed Oxidative C–H Amination of Tetrahydrofuran with Indole/Carbazole Derivatives

A simple α-C-H amination of cyclic ether with indole/carbazole derivatives has been accomplished by employing copper(II) chloride/bipy as the catalyst system. In the presence of the di-tert-butyl peroxide oxidant, cyclic ethers such as tetrahydrofuran, 1,4-dioxane, and tetrahydropyran successfully undergo C-H/N-H cross dehydrogenative coupling (CDC) with various carbazole or indole derivatives in good-to-excellent yields.

Asymmetric Hydroalkynylation of Norbornadienes Promoted by Chiral Iridium Catalysts

Across bonds: The first successful iridium-catalyzed asymmetric hydroalkynylation of nonpolar alkenes with good to excellent enantioselectivity is described (see scheme; cod = 1,5-cyclooctadiene, DCE = 1,2-dichloroethane). This catalytic system exhibits good functional group compatibility as NH(2), OH, Br, F, and SiMe(3) groups remain intact during the reaction.

A study on the substituent effects of norbornadiene derivatives in iridium-catalyzed asymmetric [2 + 2] cycloaddition reactions

Employing a series of norbornadiene derivatives as substrates, the effects of various substituents on the Ir-catalyzed asymmetric [2 + 2] cycloaddition reactions with arylacetylenes were studied. It was found that the atom forming the short bridge chain had a great effect on the enantioselectivity of the reaction. Heteroatoms, such as oxygen and nitrogen, always resulted in excellent enantioselectivity. However, carbon atoms could decrease the enantioselective control ability of the catalyst over the reaction. The groups on the unreacted carbon-carbon double bond were found to have but a little effect on the reaction. Based on the results of the experiments, a mechanism was also hypothesized for the reaction.

Oxidative coupling between C(sp2)–H and C(sp3)–H bonds of indoles and cyclic ethers/cycloalkanes

Cross-dehydrogenative-coupling (CDC) between C-H/C-H bonds of indoles and cyclic ethers/cycloalkanes is made viable through a simple transition-metal-free pathway. With the aid of only di-tert-butyl peroxide, a number of inactive cyclic ethers and cycloalkanes can be directly coupled with indole derivatives in satisfactory yields.

Rh-catalyzed highly enantioselective hydroalkynylation reaction of norbornadiene derivatives.

The complexes of various Rh precusors with ferrocenyl chiral ligand (R,S)-Cy2PF-PPh2 were found effective catalysts for the asymmetric hydroalkynylation reaction of norbornadiene derivatives. When RhCl3·3H2O was employed, good yields (up to 98%) and high enantioselectivities (up to >99.9% ee) could be obtained for the reactions of a broad scope of substrates.

Cobalt-catalyzed cross-dehydrogenative coupling of imidazo[1,2-a]pyridines with isochroman using molecular oxygen as the oxidant

A cobalt-catalyzed cross-dehydrogenative coupling of 2-arylimidazo[1,2-a]pyridines with isochroman using molecular oxygen as the oxidant is reported. A broad range of 2-arylimidazo[1,2-a]pyridines reacted smoothly to afford the corresponding products in moderate to good yields. The advantages of this method are: inexpensive catalysts, environmentally benign conditions and operational convenience.

Palladium-Catalyzed N-Arylation of Sulfoximines with Aryl Sulfonates

Palladium-catalyzed C-N bond coupling reaction between NH-sulfoximines and aryl halides (e.g., -Br, -I, and -Cl and pseudohalides -OTf and -ONf) was successfully achieved. Nevertheless, aryl tosylates/mesylates left much to be achieved. In this report, a general N-arylation of sulfoximines with aryl sulfonates is described. Using Pd(OAc)2/MeO-CM-phos complex, the N-aryl sulfoximine products can be obtained in good-to-excellent yields (up to 99%) with good common functional group compatibility. In addition to arene moieties, alkenyl tosylates are shown to be successful coupling partners.

A General Palladium-Phosphine Complex To Explore Aryl Tosylates in the N-Arylation of Amines: Scope and Limitations

The scope and limitations of the monoselective N-arylation of various amines by using aryl and hetaryl tosylates are presented. The air-stable and easily accessible Pd(OAc)2 /CM-phos {CM-phos=2-[2-(dicyclohexylphosphino)phenyl]-1-methyl-1H-indole}catalyst system was able to deal with a wide range of aryl tosylate substrates as well as amine nucleophiles, including primary and secondary cyclic/acyclic aliphatic amines and anilines. NH-Bearing heterocycles such as indole, carbazole, pyrrole, 10-phenothiazine, and 10-phenoxazine were shown to be feasible coupling partners under this catalytic system. The described reaction conditions tolerate a wide range of functional groups and allow an array of aromatic amines as well as unsymmetrical amine products to be easily accessed from the various phenolic derivatives. Interestingly, this catalyst system even offers the opportunity to perform the reaction in water medium. We also report the intermolecular coupling of optically active α-central chiral amines with aryl tosylates without erosion of the enantiomeric purity.