Palladium-Catalyzed Amide-Directed Enantioselective Hydrocarbofunctionalization of Unactivated Alkenes Using a Chiral Monodentate Oxazoline Ligand

Abstract

A Pd-catalyzed amide-directed enantioselective hydrocarbofunctionalization of unactivated alkenes with C-H nucleophiles has been developed using a chiral monodentate oxazoline (MOXin) ligand. Various indoles react at C3 position with aminoquinoline-coupled 3-alkenamides to give γ addition products in good to excellent yield and enantioselectivity. This study represents an important advance of the development of chiral monodentate oxazoline ligands, which have been underexplored for asymmetric catalysis.

Palladium(0)‐Catalyzed Directed syn‐1,2‐Carboboration and ‐Silylation: Alkene Scope, Applications in Dearomatization, and Stereocontrol by a Chiral Auxiliary

“…To complement these approaches,w er easoned that as ubstrate-directed strategy involving palladium catalysis could enhance reactivity with hindered substrates (e.g., tetrasubstituted alkenes [8] )and provide ameans of controlling regioselectivity in amanner that is independent of the alkene substitution pattern. Previously,o ur lab [9] and others [10] have developed at oolkit of hydro-and difunctionalization reactions of alkenyl carbonyl compounds bearing the 8-aminoquinoline [11] (AQ) directing group.A sp art of this effort, we described an anti-selective 1,2-carboboration of alkenyl carbonyl compounds that initiates via Wacker-type carbopalladation (Scheme 1C). [3c-e] Though useful in its own right, this method is limited in terms of the carbogenic groups that can be introduced (indole-type nucleophiles) and the alkene scope (terminal and 1,2-disubstituted alkenes).…”

Recent Progress in Transition Metal‐Catalyzed Regioselective Functionalization of Unactivated Alkenes/Alkynes Assisted by Bidentate Directing Groups

“…Recently, Chen and co‐workers successfully used the monodentate oxazoline (MOXin) as a chiral ligand for Pd(II)‐catalyzed enantioselective hydrocarbofunctionalization of internal alkenes with the assistance of 8‐aminoquinoline (Scheme ) . The chiral MOXin ligand, which could be readily prepared from simple amino acid, has been underexplored in asymmetric catalysis, and this transformation represents a significant progress in the exploration of chiral MOXin ligands.…”

Metal‐Catalyzed Substrate‐Directed Enantioselective Functionalization of Unactivated Alkenes

“…The first Pd‐catalyzed amide‐directed enantioselective hydrocarbofunctionalization of unactivated acyclic alkenes was realized by He, Peng, Chen and co‐workers through ligand design (Scheme ) . The substrate serves as a tridentate ligand for Pd center, leaving a single vacant site for chiral induction.…”