Asymmetric nucleophilic dearomatization of diazarenes by anion-binding catalysis

Enantioselective dearomatization of isoquinolines by anion-binding catalysis en route to cyclic α-aminophosphonates.

An enantioselective dearomatization of isoquinolines has been developed using chiral anion-binding catalysis. This transformation, catalyzed by a simple and easy to prepare tert-leucine-based thiourea derivative, makes use of silyl phosphite as a nucleophile and generates cyclic α-aminophosphonates. This is the first time asymmetric anion-binding catalysis has been applied to the synthesis of α...

Asymmetric Mannich Synthesis of α-Amino Esters by Anion-Binding Catalysis

We report a scalable, one-pot Mannich route to enantioenriched α-amino esters by direct reaction of α-chloroglycine ester as a practical imino ester surrogate. The reaction is promoted by a chiral aminothiourea, which is proposed to operate cooperatively by generating an iminium ion by chloride abstraction and an enolate by deprotonation, followed by highly stereoselective C-C bond formation be...

Chiral anion phase-transfer catalysis applied to the direct enantioselective fluorinative dearomatization of phenols.

Chiral anion phase-transfer catalysis has enabled the direct and highly enantioselective fluorinative dearomatization of phenols catalyzed by a BINOL-derived phosphate. The process efficiently transforms simple, readily available phenols into fluorinated chiral small molecules bearing reactive functionality under ambient reaction conditions with high enantioselectivity. The close relationship o...

Enantioselective N-heterocyclic carbene-catalyzed nucleophilic dearomatization of alkyl pyridiniums.

NHC-catalyzed nucleophilic dearomatization of alkyl pyridiniums has been achieved to generate 1,4-dihydropyridines with high enantioselectivity. This is a rare example of catalytic, asymmetric addition of a nucleophile to the activated pyridinium that prefers C-4 functionalization leading to the 1,4-dihydropyridine with high selectivity.

Hydrogen bonding and alcohol effects in asymmetric hypervalent iodine catalysis: enantioselective oxidative dearomatization of phenols.