Wenzhong Zhang

Ni-Catalyzed Reductive Cross-Coupling of Amides with Aryl Iodide Electrophiles via C–N Bond Activation

A Ni-catalyzed reductive cross-coupling reaction between two electrophiles, amides and aryl iodides, has been developed. This work is the first example using amide as an electrophile to couple with another electrophile, instead of using highly basic and pyrophoric nucleophiles. Furthermore, the Ni catalyst chemoselectively inserting the C-N bond of amide triggered the reductive cross-coupling reaction, which solves the problem that the Ni catalyst preferentially inserts the more reactive C-I bond to form a self-coupling product.

Photoredox-Catalyzed Cascade Difluoroalkylation and Intramolecular Cyclization for Construction of Fluorinated γ-Butyrolactones

A cascade visible-light photocatalytic difluoroalkylation and intramolecular cyclization reaction has been developed for the synthesis of difluoroalkylated oxygen heterocycles. The reaction was carried out under very mild conditions, affording fluorinated isobenzofuran-1-ones, lactone, and cyclic ethers with up to 97% chemical yields. Furthermore, several types of bromofluoroalkane precursors bearing ester, keto, amido, and phosphate groups could all work very well in this reaction, which provides an easy method for the preparation of functionalized difluoroalkylated oxygen heterocycles.

Catalytic Enantioselective Michael Addition Reactions of Tertiary Enolates Generated by Detrifluoroacetylation

This work describes, for the first time, Michael addition reactions of tertiary fluoro-enolates in situ generated by detrifluoroacetylation with 1-(1-(phenylsulfonyl) vinylsulfonyl)benzene. Excellent enantioselectivity and chemical yields were achieved with application of catalysts (10 mol %) derived from Cu(OTf)2 and (1S,2S)-1,2-diphenylethane-1,2-diamine. These reactions show a considerable degree of structural generality and allow the preparation of new types of biologically relevant molecules that contain quaternary C-F stereogenic carbon atoms and feature five-, six-, or seven-membered rings as well as heterocyclic 3-fluoro-2,3-dihydrochromen-4-one moieties.

Axially chiral Ni(II) complexes of α-amino acids: Separation of enantiomers and kinetics of racemization

Herein we present design, synthesis, chiral HPLC resolution, and kinetics of racemization of axially chiral Ni(II) complexes of glycine and di-(benzyl)glycine Schiff bases. We found that while the ortho-fluoro derivatives are configurationally unstable, the pure enantiomers of corresponding axially chiral ortho-chloro-containing complexes can be isolated by preparative HPLC and show exceptional configurational stability (t1/2 from 4 to 216 centuries) at ambient conditions. Synthetic implications of this discovery for the development of new generation of axially chiral auxiliaries, useful for general asymmetric synthesis of α-amino acids, are discussed.