Transition-metal-catalyzed carbonylation has emerged as a powerful and versatile strategy for efficient construction of complicated carbonyl-containing molecules from simple chemical feedstocks in the past decades. Although many transition-metals, especially noble...

New methods for preparation of chiral alkyl fluorides have been studied intensively in recent years due to the favorable physicochemical and biological properties of those structures. Herein, we describe the regio-and enantioselective allylic alkylation of α-pyridyl-α-fluoroesters with allyl acetates promoted by Cu/Pd synergistic catalysis, constructing the carbon-fluorine quaternary stereocenters. In this co-catalytic system, palladium catalyst mainly constructed the CÀ C bond, while chiral copper catalyst controlled the enantioselectivity. A series of aryl-and aliphatic-substituted allyl acetates are applied, giving the corresponding products in high yield, excellent enantioselectivity, and E/Z (up to 98% yield, 98 : 2 er, E/Z > 20 : 1).

Efficient Cu-catalyzed intramolecular Heck-borylation of alkenes was developed. Racemic and chiral boronated indolines were achieved by borarylation of alkenes with B2pin2 via simultaneous construction of C-C and C-B bonds by Cu/phosphine ligand system. With CuOAc and DPPE ligand, a series of 3-substituted borylated indoline derivatives were concisely synthesized in good to excellent yields in short time under mild conditions. Asymmetric synthesis was investigated by ligand screening, and the chiral 3-substituted borylated indoline was obtained in 80% yield and 80:20 er with (R,R)-MeDuphos. Application of 3-substituted borylated indolines has been demonstrated by a gram scale synthesis and further functionalization.