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.

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 PdA C H T U N G T R E N N U N G (OAc) 2 (palladium acetate), AgOAc (silver acetate) and KHF 2 (potassium hydrogen fluoride), could efficiently catalyze the coupling reaction in acetone without the aid of any ligand, leading exclusively to the g-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.

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The combination of Pd(TFA)2 and KOH could efficiently catalyze the reaction of β-substituted allylic halides with arylboronic acids in water.

Thei ridium-catalyzed highly regioselective transfer hydrogenation of av ariety of 2-substituted and2 ,9-disubstituted 1,10-phenanthrolines under mild conditions with formic acid as the hydrogen source is described. In the presence of ac atalytic amount of the iridium complex [Cp*IrCl 2 ] 2 , the transfer hydrogenation proceededs moothly in 1,4-dioxaneu nder ligand-free conditions,e xclusively leading to ar ange of 1,2,3,4-tetrahydro-1,10-phenanthroline productsi nh igh yields.T he catalyst generated in situ from [Cp*IrCl 2 ] 2 and (R,R)-(CF 3 ) 2 C 6 H 3 SO 2 -dpen [N-(2-amino-1,2-diphenylethyl)-3,5-bis(trifluoromethyl)benzenesulfonamide] could efficiently catalyze the asymmetric transfer hydrogenation of these 1,10-phenanthrolinesi ni sopropyl alcohol (i-PrOH)t oa fford chiral 1,2,3,4-tetrahydro-1,10-phenanthrolines in high yields with up to > 99% ee.T he key to the success of the reduction is the choice of solvent and hydrogen source.