Nickel-Catalyzed, Enantioselective Hydrofluoromethylation of Olefins: Access to Chiral α-Fluoromethylated Amides and Esters

Abstract

We herein report the nickel-catalyzed enantioselective hydrofluoromethylation of enamides and enol esters with CH 2 FI as the fluoromethyl source to enable the diversity-oriented synthesis (DOS) of chiral α-fluoromethylated amides as well as esters with features of wide functional group compatibility as well as excellent enantioselectivity. The synthetic value of this protocol was demonstrated by transformations of the resulted α-fluoromethylated amides to different scaffolds including amine, oxazoline, thiazoline, and α-fluoromethylated tetrahydroquinoline.

Silanes as a versatile hydride source for Ni–H catalysis: a promising tool for π-hydro functionalization

“…In 2023, Li, Huang and co-workers reported that a BOX ligand ( L28 ) tuned NiH-catalyzed enantioselective hydrofluoromethylation of alkenes, which afforded α-fluoromethylated amides or esters in good yields with excellent enantioselectivities (Scheme 52). 86…”

Nickel-Catalyzed Hydroamination and Hydroalkoxylation of Enelactams with Unactivated Amines and Alcohols

“…Notable successes have been obtained with CuH complexes as reported in the pioneering works of the Miura and Buchwald groups. , Furthermore, CoH ,− and FeH , complexes have also shown potential in such reactions. Due to the unique reactivity and a variety of oxidation states of nickel ranging from Ni(0) to Ni­(IV), research concerning NiH-catalyzed reactions has attracted more attention. , One research interest in this area has focused on the NiH complex-catalyzed hydroamination of alkenes with different nitrogen sources (Scheme a). For example, the groups of Hu and Wang reported the nickel-catalyzed hydroamination of alkenes with electrophilic anthranils .…”