In this review, a summary of transition metal-catalyzed C–H activation by utilizing the functionalities as directing groups is presented.

NNNifty targets: In a straightforward copper-mediated synthesis of 1,4-disubstituted and 1,4,5-trisubstituted 1,2,3-triazoles, readily available aniline N-tosylhydrazone substrates underwent cyclization through CN NN bond formation (see scheme; Piv=pivaloyl, Ts=p-toluenesulfonyl). This method enables the preparation 1,2,3-triazoles with high efficiency under mild conditions without use azides. As service to our authors readers, this journal provides supporting information supplied by...

An efficient and convenient method was developed for the preparation of 3-sulfenylindoles via a K2CO3 promoted direct sulfenylation indoles with disulfides. The is applicable to wide range containing different functional groups furnishing good excellent yields. This synthetic strategy features environmental friendliness, easy operation, mild reaction conditions.

The efficient nickel-catalyzed direct amination of arenes with simple alkylamines has been achieved the assistance a bidentate directing group through sp(2) C-H bond functionalization. Preliminary mechanistic investigations indicate that reaction probably proceeds Ni(I)/Ni(III) catalytic pathway.

Recent advances in the carbonylative synthesis of heterocycles by using diverse CO surrogates as sources are summarized and discussed.

Visible light can be used as a sole driving force for the fixation of sulfur dioxide into sulfonylated coumarins.

Abstract 1,4,5‐Trisubstituted 1,2,3‐triazoles have been regarded as highly significant nitrogen‐containing heterocycles due to their broad spectrum of biological activities and other prominent properties. Well‐established pioneering examples indicate that multicomponent reactions (MCRs) are a straightforward powerful tool for the construction various functionalized heterocyclic molecules, especially fully‐decorated 1,2,3‐triazoles. The recent progress regarding synthetic approaches towards...

We have developed a Rh( iii )-catalyzed C–H activation/chemodivergent annulation of N -carbamoylindoles with TFISYs, allowing facile access to variety trifluoromethyl-substituted (dihydro)pyrimidoindolones high efficiency. Solvents play critical role in the selectivity reaction.

CuI-catalyzed aerobic oxidative synthesis of imidazoheterocycles has been achieved. Four hydrogen atoms were removed in one step. This protocol was compatible with a broad range functional groups, and it also successfully extended to unsaturated ketones, bringing about the formation alkenyl-substituted imidazoheterocycles, which difficult prepare by previous means. Preliminary mechanistic studies indicated that this reaction most likely proceed through catalytic Ortoleva-King reaction. By...

A general and expeditious approach for the metal-free mediated synthesis of 1,3,5-trisubstituted 1,2,4-triazoles from hydrazones aliphatic amines has been achieved under aerobic oxidative conditions. The reaction proceeds through a cascade C–H functionalization, double C–N bonds formation, aromatization sequence.

An unprecedented [2+2] annulation of aldehydes with ketimines to afford enantioenriched spirooxindole β-lactams <italic>via</italic> oxidative NHC catalysis is disclosed.

Abstract A novel synthetic approach toward 1,4‐disubstituted 1,2,3‐triazoles by CN‐ and NN‐bond formation has been established under transition‐metal‐free conditions. Complete control of the regioselectivity was successfully achieved. Commercially available anilines, ketones, N ‐tosylhydrazine were treated with molecular iodine in one pot to allow regioselective generation high yields without use azides.

An FeCl3-mediated cascade coupling/decarbonylative annulation reaction for the efficient construction of 2-(trifluoromethyl)quinazolin-4(3H)-ones has been developed. This transformation employs readily available isatins and trifluoroacetimidoyl chlorides as starting materials, providing a facile practical route to diverse biologically relevant quinazolin-4(3H)-one derivatives. A plausible pathway proposed based on mechanistic observations.

A ruthenium-catalyzed peri-selective C-H activation and annulation of 1-naphthols with CF3-substituted imidoyl sulfoxonium ylides that uses hydroxyl as a weakly coordinating directing group is disclosed. The strategy provides facile practical route to diverse trifluoromethyl-containing 2,3-dihydrobenzo[de]chromen-2-amines high efficiency. Notable advantages this protocol include readily available materials, excellent regioselectivity, good functional compatibility, scalability.

An efficient and straightforward approach for the synthesis of trifluoromethyl-decorated benzo[de][1,8]naphthyridines has been achieved via Rh(III)-catalyzed dual C-H activation cascade annulation benzimidates CF3-imidoyl sulfoxonium ylides. The novel transformation involves formation four new chemical bonds along with release two molecules dimethyl sulfoxide (DMSO) one molecule each ethanol amine. optoelectronic properties obtained fused aromatic products have investigated by recording...

A straightforward strategy for the metal-free construction of trifluoromethyl-containing pyrazole derivatives has been achieved from readily available α-halo hydrazones and CF3-imidoyl sulfoxonium ylides. The cascade transformation proceeds through formal [4+1] cycloaddition followed by an unexpected dual double bond isomerization. protocol features mild conditions, easy operation, excellent substrate compatibility, good regioselectivity. synthetic utility is demonstrated scale-up reaction...

Abstract An approach for the construction of 5‐trifluoromethyl‐1,4‐dihydro‐1,2,4‐triazines has been developed via base‐mediated [3+3] cycloaddition in‐situ generated nitrile imines and CF 3 ‐substituted imidoyl sulfoxonium ylides. The metal‐free protocol is characterized by readily available starting materials, mild conditions, a broad substrate scope, high efficiency, good synthetic prospect, scalability. magnified image

A rhodium(III)-catalyzed aldehydic C(sp

Abstract An effective copper‐mediated synthesis of 1,5‐dialkyl‐4‐aryl‐1,2,3‐triazoles and 1,4‐dialkyl‐5‐aryl‐1,2,3‐triazoles has been achieved by the use different N ‐tosylhydrazones alkyl amines. The scope substrates could be extended from anilines to aliphatic amines when 30 mol % amino acid is added into reaction mixture. This methodology exhibits many notable features, such as broad scope, high efficiency, good regioselectivity. Preliminary mechanistic studies indicated that probably...

An efficient and expeditious protocol for the synthesis of diverse difunctionalized indenones through rhodium-catalyzed C–H activation multistep cascade reaction benzimidates alkenes has been developed. The transformation involves cleavage formation multiple bonds in one pot under mild conditions, Mn(OAc)2 plays an important role reaction.

A 1-hydroxybenzotriazole-assisted, N-heterocyclic carbene catalyzed direct β-functionalization of saturated carboxylic esters is disclosed. This formal [3 + 2] annulation reaction with isatins affords optically pure spirooxindole lactones (on gram scale) bearing two vicinal stereogenic centers. dual role HOBt proposed based on controlled experiments to rationalize the enhancement diastereoselectivity and enantioselectivity.

The rapid and convenient construction of benzo-fused cyclic compounds has attracted significant attention due to their wide applications in various fields. As important building blocks organic synthons, aryltriazene can be applied the synthesis a variety heterocycles carbocycles. With promotion by Lewis or Brønsted acids, aryltriazenes are readily transformed into reactive aryl cations which undergo intramolecular cyclization form diverse compounds. This account covers recent developments...

A nickel-catalyzed stereoselective alkenylation of an unactivated β-C(sp3)-H bond in aliphatic amide with terminal alkynes using 8-aminoquinoline auxiliary is reported for the first time. This reaction displays excellent functional group tolerance respect to both amides and features a cheap nickel catalytic system. The 8-aminoquinolyl directing could be smoothly removed, resultant β-styrylcarboxylic acid derivatives serve as versatile building blocks further transformation.

A new method of cobalt-catalyzed annulation anilides and internal alkynes for the efficient synthesis quinoline scaffolds was developed.