The research in the field of asymmetric carbene organic catalysis has primarily focused on the activation of carbon atoms in non-aromatic scaffolds. Here we report a reaction mode of carbene catalysis that allows for aromatic aldehyde activation and remote oxygen atom functionalization. The addition of a carbene catalyst to the aldehyde moiety of 2-hydroxyl aryl aldehyde eventually enables dearomatization and remote OH activation. The catalytic process generates a type of carbene-derived intermediate with an oxygen atom as the reactive centre. Inexpensive achiral urea co-catalyst works cooperatively with the carbene catalyst, leading to consistent enhancement of the reaction enantioselectivity. Given the wide presence of aromatic moieties and heteroatoms in natural products and synthetic functional molecules, we expect our reaction mode to significantly expand the power of carbene catalysis in asymmetric chemical synthesis.

An unprecedented N-demethylation of N-methyl amides has been developed by use of N-fluorobenzenesulfonimide as an oxidant with the aid of a copper catalyst. The conversion of amides to carbinolamines involves successive single-electron transfer, hydrogen-atom transfer, and hydrolysis, and is accompanied by formation of N-(phenylsulfonyl)benzenesulfonamide. Carbinolamines spontaneously decompose to N-demethylated amides and formaldehyde, because of their inherent instability.Letter pubs.acs.org/OrgLett

This review summarizes recent progress in catalytic asymmetric construction of 1,2,3,4-tetrahydroisoquinolines and 3,4-dihydroisoquinolines, among the most important “privileged scaffolds”.

A CuBr 2 -promoted cyclization and bromination of arene-alkyne substrates has been developed, affording 9-bromophenanthrene derivatives highly efficiently. This reaction provides a novel and efficient protocol for C-Br bond formation from an inorganic bromine source via the reductive elimination of the Cu(III) species.Scheme 1 Some carbon-halogen bond formation reactions. † Electronic supplementary information (ESI) available. CCDC 1438272. For ESI and crystallographic data in CIF or other electronic format see

Here, we demonstrate that merging photoredox catalysis with Lewis acid catalysis provides a fundamentally new activation mode of C-C triple bonds, to achieve the bond-forming reaction of alkynes with weak nucleophiles. Using a synergistic merger of Eosin Y and Cu(OTf)2, a highly efficient cyclization reaction of arene-ynes was developed.