An asymmetric Mannich reaction of phenylacetate thioesters and sulfonylimines using cinchona alkaloid-based amino (thio)urea catalysts is reported that employs proximity-assisted soft enolization. This approach to enolization is based on the cooperative action of a carbonyl-activating hydrogen bonding (thio)urea moiety and an amine base contained within a single catalytic entity to facilitate i...

N-heterocyclic carbene-catalyzed reactions for the formation of aromatic compounds are reviewed. The subdivided into 4 types based on their activation modes. A brief summary achievements and challenges remaining in carbene (NHC)-catalyzed arene construction processes is provided at end this review. An outlook future research direction within field also given our own opinion knowledge trends dev...

In this communication, we describe p-xylene oxidation with molecular oxygen at 373 K and atmospheric pressure using N-hydroximide catalysts. p-Xylene conversion was rather high over the first 2 h of reaction and complete by the end of the experiment. The product distribution curves versus reaction time are typical of consecutive reactions. The main intermediate product is p-toluic acid. Peak co...

Cinchona alkaloids with a free 6'-OH functionality are being increasingly used within asymmetric organocatalysis. This fascinating class of bifunctional catalyst offers a genuine alternative to the more commonly used thiourea systems and because of the different spacing between the functional groups, can control enantioselectivity where other organocatalysts have failed. In the main, this revie...

The direct, asymmetric α-amination of aldehydes has been accomplished via a combination of photoredox and organocatalysis. Photon-generated N-centered radicals undergo enantioselective α-addition to catalytically formed chiral enamines to directly produce stable α-amino aldehyde adducts bearing synthetically useful amine substitution patterns. Incorporation of a photolabile group on the amine p...

The organocatalysis-based dynamic kinetic resolution (DKR) process has proved to be a powerful strategy for the construction of chiral compounds. In this feature review, we summarized recent progress on the DKR process, which was promoted by chiral bifunctional (thio)urea and squaramide catalysis via hydrogen-bonding interactions between substrates and catalysts. A wide range of asymmetric reac...

Reactions that form a C-C bond make up a foundational pillar of synthetic organic chemistry. In addition, organocatalysis has emerged as an easy, environmentally-friendly way to promote this type of bond formation. Since around 2000, organocatalysts have been used in a variety of C-C bond-forming reactions including Michael and aldol additions, Mannich-type reactions, and Diels-Alder reactions,...

A new concept in organocatalysis allowing for the construction of cyclobutanes with four contiguous stereocenters with complete diastereo- and enantiomeric control by a formal [2 + 2]-cycloaddition is presented. The concept is based on simultaneous dual activation of α,β-unsaturated aldehydes and nitroolefins by amino- and hydrogen-bonding catalysis, respectively. A new bifunctional squaramide-...