Although the pentafluorosulfanyl group was regarded as a “substituent of the future” due to its unique structural and electronic features and potential medicinal properties, there are still a very limited number of methods to accesses SF₅-containing heterocycles. Herein, we present an efficient one-pot tandem SF₅-quinoline synthetic method. Iron(III) was employed as the catalyst for the three-component coupling reaction of SF₅-anilines, aldehydes and alkynes. The reaction was performed in the presence of air and a series of 6- or 7-SF₅-substituted quinolines were obtained in good yields.

The Pd(OAc)₂-catalyzed direct CH bond olefination of unreactive arenes with allylamines in the presence of AgOAc was developed. A variety of allylamines including β-substituted substrates underwent smooth coupling reactions with various arenes to give exclusively the terminal arylation products in high yields with excellent regioselectivities and stereoselectivities. The reaction is compatible with a range of functional groups in both coupling partners. The carbonyl group in the allylamine substrates is critical to catalysis, and the high regio- and stereocontrol observed is attributed to coordination between the carbonyl O and Pd atoms.

A Rh^I-catalyzed direct C2-arylation of indoles with diversely substituted aryl carboxylic acids has been developed using 2-pyrimidyl group as an easily installable and readily removable N-directing group. The reaction proceeded smoothly without the need for any external oxidants under relatively mild conditions to produce the C2-arylated indoles in high yields with excellent regioselectivity. A range of functional groups in both coupling partners were tolerated regardless of their electronic properties and positions. With the assistance of the 2-pyrimidyl group, these C2-functionalized products could further undergo C7-arylation to give the C7-aryl indole products. Mechanistic evidence supports that the reaction involves a decarbonylation step, and the carboxylic acids could be activated in situ by treatment with (tBuCO)₂O to generate the active anhydrides.

Palladium catalyst systems for the regioselective Mizoroki–Heck arylation of N,N-diprotected and N-protected allylamines with aryl chlorides have been developed. Pd(OAc)₂ in combination with appropriate additives could efficiently catalyze the linear arylation of N,N-diprotected allylamines with aryl chlorides in toluene to give exclusively the γ-arylated products in good to excellent yields and with excellent regio- and stereocontrol and good functional group tolerance. With use of a catalytic mixture of Pd(OAc)₂ and 1,1'-bis(diphenylphosphino)ferrocene, the arylation of N-protected allylamines with aryl chlorides could be accomplished in ethylene glycol/DMSO, which afforded complete β-regioselectivity with good functional group tolerance. The steric and electronic properties of allylamine substrates are found to be critical to the catalytic activity and regiocontrol in both linear and internal arylations.

A general and convenient palladium-catalyzed oxidative Heck arylation of both N-protected and N,N-diprotected allylic amines with arylboronic acids under mild conditions has been developed. The catalyst system, consisting of Pd(OAc)₂ (palladium acetate), AgOAc (silver acetate) and KHF₂ (potassium hydrogen fluoride), could efficiently catalyze the coupling reaction in acetone without the aid of any ligand, leading exclusively to the γ-arylated allylic amine products in good to excellent yields. This method is highlighted with excellent regio- and stereocontrol and remarkable functional group tolerance. The carbamate moiety in allylic amine substrates is of crucial importance to the catalytic performance, and the chelation between the carbonyl O (oxygen) and Pd (palladium) atoms is believed to be responsible for the high regioselectivity and stereoselectivity observed.

A palladium-catalyzed highly regioselective and stereoselective direct arylation of allylamine derivatives with a wide range of thiophenes and furans has been developed. In the presence of palladium(II) acetate [Pd(OAc)₂] catalyst and appropriate oxidants, the coupling reaction proceeded with excellent group compatibility and high efficiency, leading exclusively to γ-arylated linear (E)-allylamines. It was found that the choice of solvent, olefin substrate and oxidant had an important influence on reaction efficiency, and the use of sterically demanding N,N-diprotected allylamines bearing a carbamate moiety is crucial for securing high regioselectivity and stereoslectivity. This method provides a straightforward approach for the efficient synthesis of various γ-heteroarylated, linear (E)-allylamines.

The highly efficient and regioselective palladium-catalyzed Heck coupling of aryl bromides with electron-rich allylamine derivatives is described. It was found that the choice of solvent, olefin, ligand and additive had a fundamental influence on the regioselectivity and reactivity of the reaction. The combination of palladium acetate [Pd(OAc)₂] and 1,3-bis(diphenylphosphino)propane (dppp) in ethylene glycol (EG) constitutes a highly effective catalyst system for internal arylation of N-Boc-allylamine (tert-butyl methyl allyliminodicarbonate) with aryl bromides to give good to excellent regioselectivities, while the catalyst system consisting of Pd(OAc)₂, tetrabutylammonium bromide (TBAB) and 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) additive allows for a variety of aryl bromides to react efficiently with N,N-(Boc)₂-allylamine (di-tert-butyl allyliminodicarbonate) in water to exclusively afford the linear (E)-allylamine products in high yields.

The use of a chiral iridium catalyst generated in situ from the (cyclooctadiene)iridium chloride dimer, [Ir(COD)Cl]₂, the P-Phos ligand [4,4′-bis(diphenylphosphino)-2,2′,6,6′-tetramethoxy-3,3′-bipyridine] and iodine (I₂) for the asymmetric hydrogenation of 2,6-substituted quinolines and trisubstituted pyridines [2-substituted 7,8-dihydroquinolin-5(6H)-one derivatives] is reported. The catalyst worked efficiently to hydrogenate a series of quinoline derivatives to provide chiral 1,2,3,4-tetrahydroquinolines in high yields and up to 96% ee. The hydrogenation was carried out at high S/C (substrate to catalyst) ratios of 2000–50000, reaching up to 4000 h⁻¹ TOF (turnover frequency) and up to 43000 TON (turnover number). The catalytic activity is found to be additive-controlled. At low catalyst loadings, decreasing the amount of additive I₂ was necessary to maintain the good conversion. The same catalyst system could also enantioselectively hydrogenate trisubstituted pyridines, affording the chiral hexahydroquinolinone derivatives in nearly quantitative yields and up to 99% ee. Interestingly, increasing the amount of I₂ favored high reactivity and enantioselectivity in this case. The high efficacy and enantioselectivity enable the present catalyst system of high practical potential.