A palladium-catalyzed fluoroalkylative cyclization of olefins with readily available R-I reagents to afford the corresponding fluoroalkylated 2,3-dihydrobenzofuran and indolin derivatives with moderate to excellent yields is reported. This novel procedure provides an efficient method for the construction of C-CF and C-O/N bonds in one step. A wide range of functional groups are tolerated. It is proposed that a radical/SET (single electron transfer) pathway proceeding via the fluoroalkyl radical may be involved in the catalytic cycle.

A Pd -catalyzed asymmetric aminohydroxylation of 1,3-dienes with N-tosyl-2-aminophenols was developed by making use of a chiral pyridinebis(oxazoline) ligand. The highly regioselective reaction provides direct and efficient access to chiral 3,4-dihydro-2H-1,4-benzoxazines in high yield and enantioselectivity (up to 96:4 e.r.). The reaction employs readily available N-tosyl-2-aminophenols as a unique aminohydroxylation reagent and is complementary to known asymmetric aminohydroxylation methods.

Allylamines are important building blocks in the synthesis of bioactive compounds. The direct coupling of allylic CÀ H bonds and commonly available amines is a major synthetic challenge. An allylic CÀ H amination of 1,4-dienes has been accomplished by palladium catalysis. With aromatic amines, branchselective allylic aminations are favored to generate thermodynamically unstable Z-allylamines. In addition, more basic aliphatic cyclic amines can also engage in the reaction, but linear dienyl allylic amines are the major products.

Mimicking the way nature synthesizes organic molecules, multi-catalyst relay catalysis (MCRC), based on the seamless combination of a series of catalytic reactions, has emerged as a promising strategy for achieving ideal synthesis. In such systems, each step takes place orderly and sequentially. Taken as a whole, the entire process appears indistinguishable from a common one-step reaction but provides a means for extraordinary transformations. Here, we report a onestep transformation of styrenes, allylic alcohols, and syngas to a-quaternary chiral aldehydes in a multi-catalyst system consisting of a rhodium(I) complex, a palladium(0) complex, a chiral Brønsted acid catalyst, and an achiral amine (20-100 mol %). The cascade hydroformylation and asymmetric allylation reaction was realized with high yields (up to 98%) and high enantioselectivities (up to 99% ee) under mild conditions (1 bar of syngas).