Chiral Hemilabile P,N‐Ligand‐Assisted Gold Redox Catalysis for Enantioselective Alkene Aminoarylation

Abstract

Enantioselective, intermolecular alkene arylamination was achieved through gold redox catalysis. Screening of ligands revealed chiral P,N ligands as the optimal choice, giving alkene aminoarylation with good yields (up to 80 %) and excellent stereoselectivity (up to 99 : 1 er). As the first example of enantioselective gold redox catalysis, this work confirmed the feasibility of applying a chiral ligand at the gold(I) stage, with the stereodetermining step (SDS) at the gold(III) intermediate, thus opening up a new way to conduct gold redox catalysis with stereochemistry control.

Hemilabile MIC^N ligands allow oxidant-free Au(i)/Au(iii) arylation-lactonization of γ-alkenoic acids

“… 58 Very recently, Shi and Patil groups developed new chiral-hemilabile P^N-ligands to access enantioselective Au( i )/Au( iii ) catalysis. 59,60 …”

Gold-catalyzed multicomponent reactions

“…cross-coupling reactivity and carbophilic activity, a novel interplay mode has been developed to achieved several 1,2-difunctionalization reactions. 83…”

Gold-Catalyzed Heck Reaction

“…Based on the gathered experimental evidence and literature reports, − ,, we initially proposed a reaction mechanism that accounts for the formation of the observed product . Further, to get a deeper insight into the regioselectivity, DFT computations were performed with the Gaussian 16 set of program using 1a and 4-iodoanisole as model substrates (Figure ).…”

“…Over the past 15 years, Au­(I)/Au­(III) redox catalysis has emerged as one of the most dynamic areas of research . A number of gold-catalyzed cross-coupling and 1,2-difunctionalization reactions have been developed by utilizing external oxidants, ,, photocatalysts, ,,, EBX reagents, ,, an electrochemical or ligand-enabled approach. ,, Even, very recently, our group and Shi’s group reported the first example of enantioselective Au­(I)/Au­(III) redox catalysis . In spite of such significant advancements, the gold-catalyzed Heck reaction which is also supposed to operate via Au­(I)/Au­(III) redox catalysis has not been realized yet.…”