In this review, the versatile and rich chemistry for the electrochemical reduction of substrates involving N,O bonds is surveyed. By the cathodic treatment of nitro, nitroso and other oxygenated nitrogen organic substrates, versatile and reactive intermediates are formed which can be subsequently converted to high value‐added products. In many examples, nitrogen heterocycles are selectively formed

A synthesis of chiral tetrahydroindoles has been developed via a Pd‐catalyzed asymmetric allylic substitution annulation using unstable enolizable ketimines as nucleophiles and our previously developed tBu‐RuPHOX as a chiral ligand. The reaction proceeds via an asymmetric desymmetrization of the meso‐diacetatecycloalkenes, providing the desired chiral tetrahydroindoles in moderate to good yields and

The catalytic asymmetric halohydroxylation of α,β‐unsaturated ketones with water as the nucleophile has been realized by applying a chiral N,N'‐dioxide/Fe(OTf)2 complex as the catalyst. Bromo‐, chloro‐ and iodohydroxylations were all suitable in this catalytic system. A variety of α‐halo‐β‐hydroxy ketones were obtained in good yields with outstanding dr and ee values. Besides, a Michael/α‐halogenation

A copper‐catalyzed asymmetric cyano(fluoro)alkylation reaction of alkenes is reported. A range of chiral fluoroalkyl cyanides were obtained in high yields and excellent enantiomeric excess from readily available chemicals. The method uses fluoroalkyl iodides as the fluoroalkyl source and employs mild conditions. The peroxide LPO plays a significant role in promotion of this radical asymmetric reaction

Selective reduction of esters to alcohols is accomplished through Mn(I)‐mediated hydrosilylation reaction. The manganese tricarbonyl complex [Mn(bis‐NHC)(CO)3Br] resulted an active pre‐catalyst for the reduction of a variety of esters using phenylsilane and the cheap and readily available polymethylhydrosiloxane. An in situ examination of the catalytic reaction using 55Mn NMR spectroscopy allow us

Cobalt‐catalyzed reductive carboxylation of aryl bromides with carbon dioxide has been developed. The reaction proceeded under one atm pressure of CO2 at 40 °C in the presence of cobalt iodide/2,2'‐bipyridine catalysts and zinc dust as a reducing reagent. Various aryl bromides could be converted to the corresponding carboxylic acids in good to high yields. Preliminary mechanistic experiments ruled

Enantioselective allylation of aldehydes and ketones is a widely used approach for preparing chiral homoallylic alcohols, however, most of the reactions are still mainly performed in organic solvents. Considering their environmental impact, expansion of synthetic technology in water has the highest priority in the organic chemistry field. Here, we report enantioselective reaction of water‐stable amido‐functionalized

Reported herein is an environmentally benign electrochemical C‐H bond dehydrogenative amination protocol for the construction of privileged carbazole moiety with broad generality. Preliminary mechanistic investigations implied a radical reaction pathway. Compared with traditional ionic routes, the scalable transition‐metal and exogenous‐oxidant free strategy highlighted the green and sustainable nature

In this work, a type of enantiopure chiral phosphines bearing a polar S=O sulfinyl group as the chiral unit in the molecule has been developed, which can be prepared in either enantiomeric form from commercially available materials by a three‐step route. The enantiopure chiral phosphines can catalyse enantiodivergent asymmetric [4+1] annulation reactions of α,β‐unsaturated imines and allylic carbonates

Abstract. Amine dehydrogenases (AmDHs) catalyze the enzymatic reduction of ketones to amines, serving as a suitable biocatalytic route for amine synthesis. A limited number of experimentally validated native AmDHs (nat‐AmDHs) have been reported recently, expanding the sequences with this function to complement the small set of engineered enzymes. Since researchers can now probe into the vast diversity

A copper catalytic addition of alkynes to phthalazin‐2‐ium bromide has been developed under mild conditions, leading to the production of propargylamines analogues. The addition products of a broad scope of phthalazin‐2‐ium bromides bearing various N‐benzyl or alkyl can be obtained in good to high yields. Moderate enantioselectivity was observed in preliminary screening studies of chiral organic ligand

A rhodium(III)‐catalyzed C(sp3)−H alkenylation of 8‐methylquinolines with electron‐deficient maleimides has been accomplished with the combination of copper acetate, 2,2,6,6‐tetramethylpiperidine‐1‐oxyl and oxygen as the oxidant. A variety of maleimides react with various 8‐methylquinolines to furnish the corresponding alkenylated products in moderate to good yields.

Oxazol‐2‐amines were synthesized by annulation of α‐amino ketones and isothiocyanates. This sequential synthetic process involves addition of α‐amino ketones to isothiocyanates and I2‐promoted desulfurative cyclization omitting isolation of the less stable thiourea intermediates. It is transition metal‐free and operationally simple, providing access to a variety of 2‐amino substituted oxazole derivatives

An ammonium ylide mediated access towards trans‐β,γ‐disubstituted‐, all‐trans‐α,β,γ‐trisubstituted‐, and α,α,β,γ‐tetrasubstituted γ‐butyrolactones bearing a broad variety of functionalities was developed. Starting from widely accessible benzylidene Meldrum’s acid derivatives and α bromo carbonyl compounds, γ butyrolactones were obtained in yields between 32–99% with up to excellent diastereoselectivities

The electrochemical synthesis of N, N’‐disubstituted benzimidazolones from ureas through an intramolecular anodic dehydrogenative N‐H/C‐H coupling has been developed. The reaction undergoes under the undivided electrolysis conditions and obviates the need for any catalysts and chemical oxidants.

A three‐component transition‐metal‐free aerobic method for the generation of 1,4‐benzothiazines is reported herein. The KI/DMSO/O2 system was found to be effective for the oxidative cyclization/coupling of 2‐aminobenzenethiols, anilines, and methylketones. Hence, various structurally important imino 1,4‐benzothiazines were assembled with broad functional group tolerance. Mechanistic studies revealed

This review updates the emerging field of enantioselective multicatalyzed tandem reactions published since the beginning of 2015. It illustrates how much the combination of different types of catalysts allows unprecedented enantioselective one‐pot reactions of many types to be achieved, allowing a direct access to a variety of very complex chiral molecules.

Single electron oxidation of electron‐rich alkenes using the iron(III)‐phenanthroline complex produced electrophilic alkene radical cations, which promoted efficient radical cation [2+1] cycloaddition reactions with diazo compounds. Subsequent chain propagation afforded tri‐ and tetra‐substituted cyclopropanes. This methodology was also expanded to [3+2] cycloaddition reactions with vinyl diazoesters

A scalable catalytic synthesis method using commodity chemicals for constructing diaryl thioethers directly from sodium arylsulfinates and iodoarenes is reported in this study. In the presence of CuO or other copper salts such as Cu(OAc)2 as well as palladium catalysts, DABCO demonstrated to be essential to promote this transformation. Various iodoarenes and aryl sulfinates were examined and demonstrated

We report here a stereoselective [3+2] cyclization of 5‐alkenyl thiazolones and ketimines that allows the assembly of three diastereoisomers through the combination of stereodivergent organocatalysis and the following diastereoselective transformation of products. A broad spectrum of pyrrolidinyl spirooxindoles featuring stereochemical diversity has been synthesized through organocatalytic formal 1

Structurally fused heterocycles encompassing 4H‐pyran centerpiece are prevalent scaffolds with promising biological activities, but have daunting synthetic challenges. Herein, we presented a regio‐ and stereoselective [4 + 2] annulation of isoindigo derivatives with allenes by bifunctional phosphonium catalysis. This protocol provides a complementary way for accessing complex heterocyclic compounds

The enantioselective synthesis of chiral azaarenes by rhodium‐catalyzed asymmetric conjugate addition of organoboronic acids to carbonyl‐activated alkenyl azaarenes was reported. Diverse chiral azaarenes were produced in up to 99% yield and with up to 99% ee (>60 examples). Catalytic asymmetric syntheses of dexchlorpheniramine and dexbrompheniramine were realized by using the developed method.

Functionalised N‐heterocyclic pyridinium N‐aminides have been designed and synthesised to evaluate a nitrenoid‐based annulation strategy into imidazole‐fused oxo‐substituted frameworks of importance to medicinal and agrochemical discovery programmes. Sulfenyl substituted ynamides were identified as privileged reactants affording productive gold‐catalysed annulation reactions with these and other nitrenoids

Metal‐free catalysts based on 1,3‐bis(carboxymethyl)imidazolium halides mediate the reaction between allylic alcohols and anilines, providing the corresponding N‐, 2‐ and 4‐allylaniline isomers selectively. The imidazolium counterion plays a crucial role in the outcome of the reaction. Thus, while the imidazolium chloride selectively provides the N‐substituted aniline, the bromide and iodide imidazolium

A synthetic route to [3.4]‐spirooxindoles based on cascade carbopalladation reactions of 1,4‐dienes is described. While carbopalladation of alkenes have been used to access mainly [4.4]‐ or [4.5]‐spirocycles, 4‐exo‐trig carbopalladation has not been yet applied to the synthesis of relevant [3.4]‐spirooxindole scaffolds bearing a cyclobutyl ring. In addition, the cascade reaction generates an exocyclic

Reaction of N‐arylsulfonyl allylamines with alkyl nitriles in the presence of di‐tert‐butyl peroxide (DTBP) and a catalytic amount of copper salt afforded homologated aziridines in good to excellent yields. A sequence involving addition of the in situ generated cyanomethyl radical to the double bond followed by a copper‐mediated intramolecular C‐N bond formation accounted for the reaction outcome.

A synthetic approach of isoindolinones through intramolecular amidation of ortho‐vinyl benzamides was reported. A variety of N‐aryl isoindolinone derivatives were prepared in moderate to excellent yields using perfluorobutyl iodide as oxidant.

1,3‐difunctionalization of cyclopropane is a useful organic transformation. The corresponding 1,3‐difunctionalized products are synthetic synthons and building blocks in Many existing ring‐opening difunctionalization methodologies rely primarily on the use of donor–acceptor cyclopropanes, while the difunctionalization of unactivated cyclopropanes is less exploited. In this research, 1,3‐bromoesterification

Abstract. Isochroman scaffold constitutes an important structural unit, which is present in various bioactive natural products and synthetic pharmaceutical compounds exhibiting wide arrays of biological properties. Hence the synthesis of this class of heterocyclic compounds in stereoselective fashion is highly significant and desirable. In the last decade, a substantial advancement has been witnessed