Intermolecular annulation reactions of 1-aryl-2-naphthols with internal alkynes proceed efficiently in the presence a Ru catalyst and Cu oxidant to generate spirocyclic compounds by sequential cleavage C(sp2)-H bond, migratory insertion alkyne, dearomatization naphthyl ring. Various molecules bearing an all-carbon quaternary stereocenter could be obtained this novel method good yields excellent regioselectivity, current process tolerates variety synthetically important functional groups.

The first dynamic kinetic asymmetric transformation of racemic biaryl substrates on the basis axial-to-central chirality transfer has been realized. Chiral Pd-NHC complexes were found to catalyze spiroannulation 4-(2-bromoaryl)-naphthalen-1-ols (or 2'-bromo-[1,1'-biphenyl]-4-ols) with internal alkynes, affording a series enantioenriched spirocyclic products bearing an all-carbon quaternary stereocenter in good yields (up 95%) excellent enantioselectivities 97% ee).

Abstract Catalytic asymmetric aminative dearomatization of 1‐substituted 2‐naphthols was successfully implemented with electrophilic azodicarboxylates under the catalysis chiral Sc III /pybox complexes. This intermolecular reaction represents a hitherto unknown enantioselective CN bond‐forming process through direct phenolic compounds to generate nitrogen‐containing quaternary carbon stereocenters.

Abstract A novel palladium(II)‐catalyzed [5+2] oxidative annulation of readily available o ‐arylanilines with alkynes has been developed for building a seven‐membered N‐heterocyclic architecture containing biaryl linkage. This method is applicable to wide range unprotected and internal alkynes, results in the chemoselective preparation imine‐containing dibenzo[ b , d ]azepines high yields excellent diastereoselectivity respect two types stereogenic elements.

A novel ruthenium-catalyzed [5 + 1] annulation of 2-alkenylanilines with sulfoxonium ylides was developed for the rapid assembly highly functionalized quinolines. This new catalytic process employs challenging but synthetically ideal free amino functionality to achieve alkenyl C–H activation as one-carbon coupling partners. Various 2-acylquinolines could be obtained good yields and excellent functional group tolerance. Moreover, potential synthetic application this methodology exemplified by...

A rhodium(<sc>iii</sc>)-catalyzed formal C–H [5 + 1] cyclization of 2-pyrrolyl/indolylanilines with vinylene carbonate has been explored towards the potent assembly diverse 4-methylpyrrolo[1,2-<italic>a</italic>]quinoxalines.

As a class of rising electrophilic coupling reagents, aryl–thianthreniums (aryl-TTs) have been gaining immense attention. Herein, novel palladium-catalyzed domino annulation aryl-TTs with anhydrides is proposed to rapidly assemble collection highly functionalized fluorenones. This finding presents an innovative reaction pattern wherein the version first involved. Heavily compared existing conversions aryl-TTs, this identified process successively functions as four aryl C–H bonds.

An intermolecular spiroannulation reaction of appropriately substituted 2-arylphenols with internal alkynes has been developed by using a Ru(II) catalyst and an oxidant. This transformation was realized phenol-directed C-H activation, migratory insertion the alkyne, subsequent dearomatization phenolic ring, providing broad range highly functionalized spirocyclic compounds in moderate yields high regioselectivity.

Here we report a novel Rh-catalyzed C−H/C−H alkenylation of N-arylmethanimines with vinylene carbonate acting as unit. Forty examples C3,C4-nonsubstituted quinolines were achieved from commercially available starting materials. This identified process features an exceedingly simple system, lower loading catalyst, and the capacity for postfunctionalization bioactive molecules.

Herein, a copper(I)-catalyzed asymmetric hydrophosphination of 3,3-disubstituted cyclopropenes is reported. It provides series phosphine derivatives in high to excellent diastereo- and enantioselectivities. The methodology enjoys broad substrate scope on both diarylphosphines. stereoselectivity attributed the stability Cu(I)-(R,R)-QUINOXP* complex presence stoichiometric HPPh2 produced phosphines, high-performance induction complex. Finally, method used for synthesis new chiral...

A microwave-assisted Pd(0)-catalyzed alkyne migratory insertion/β-naphthol dearomatization cascade process has been accomplished to access a variety of spirocyclic compounds bearing all-carbon quaternary stereogenic centers in high yields with excellent chemoselectivities.

Abstract A convenient radical cascade cyclization of aniline‐linked 1,7‐enynes with 1,3‐dicarbonyl compounds was developed to synthesize cyclopenta[ c ]quinolines in the presence AgNO 3 /K 2 S O 8 . wide range were prepared moderate excellent yields. magnified image

Vinylene carbonate (VC) has emerged as a promising coupling partner to participate in various attractive C–H conversions and implement an increasing number of novel reactions. In this review, we provide summary the advancements achieved metal-catalyzed functionalization using VC.

A new example of deuteration, involving ruthenium-catalyzed monodeuterium-methylenation indole units with vinylene carbonate, is described. This reaction was used to build an array promising highly deuterated bisindolylmethanes (d-BIMs). methodology featured excellent functional group compatibility diverse substrate categories such as indoles, N,N-dialkylanilines, and 1,3-dicarbonyls well having showcased the distinct chemical function VC innovative methylene precursor.

A divergent denitrogenation/recyclization of 1,2,3,4-benzothiatriazine-1,1-dioxides is disclosed, including C(sp 2 )-alkyl transposition and aniline dearomatization.

Pyrrolo[1,2‐a]quinoxalines and pyrrolo[1,2‐a]quinoxalin‐4(5H)‐ones are recognized as important tricyclic scaffolds due to their diverse pharmacological activities, including anticancer, anti‐fungi, anti‐tuberculosis, antimalarial, well roles 5‐HT3 receptor agonists kinase inhibitors targeting CK2 AKT, others. Developing efficient reliable synthetic approaches access these compounds remains an attractive goal in contemporary medicinal chemistry drug discovery. This review highlights recent...

Chemical utilization of carbon dioxide (CO2) has emerged as a sustainable access for synthesizing high-value chemicals. Continuously designing the more practical reaction systems is large importance. Herein, an unprecedented and powerful copper-PMHS reductive system o-aminobenzamides with CO2 disclosed. Synthetically, diverse range quinazolinones (>70 examples) are rapidly assembled excellent functional group tolerance in good yields. Moreover, building other types heterocycles such...

A new catalytic conversion type of nitro substrate with CO2 as a single-carbon source is presented, wherein great collection azaheterocycles generated by newly established iridium-catalyzed, copper-induced reductive system. This procedure handily employs poly(methylhydrosiloxane) (PMHS) the reductant to simultaneously realize dual reduction highest oxidation-state and units in one operation. Elaborate mechanistic studies illustrate essential role iridium catalyst reducing NO2 moiety well...

A metal- and external oxidant-free [3 + 2] annulation of N-amino(iso)quinoline salts with vinyl acetate as the acetylene surrogate under simple mild reaction conditions is described. series valuable pyrazolo(iso)quinoline scaffolds were synthesized through this process. Mechanistic investigations revealed that proceeds a Mannich/cyclization/aromatization sequence. Furthermore, scale-up experiments derivative syntheses product conducted.

Abstract Catalytic asymmetric aminative dearomatization of 1‐substituted 2‐naphthols was successfully implemented with electrophilic azodicarboxylates under the catalysis chiral Sc III /pybox complexes. This intermolecular reaction represents a hitherto unknown enantioselective CN bond‐forming process through direct phenolic compounds to generate nitrogen‐containing quaternary carbon stereocenters.

A highly chemoselective domino condensation/aza-Prins cyclization/retro-aldol between 2-alkenylanilines with β-dicarbonyl compounds under metal-free conditions was accomplished, giving a large category of valuable 2-substituted quinolines in good yields excellent functional group toleration. This newly established process, adopting β-ketoesters as masked C1 synthons via C-C cleavage, could even be simplified into three-component [3 + 2 1] version consisting exceedingly low-priced commercial...

Highly efficient Ni@C-400 catalyst for selective hydrogenation of phenol to cyclohexanol was developed from Ni-MOF-74.

Chemical transformation with vinylene carbonate as an emerging synthetic unit has recently attracted considerable attention. This report is a novel conversion pattern carbonate, in which such vibrant reagent unprecedentedly acts difunctional coupling partner to complete the C-H annulation of free anilines. From commercially available substrates, this protocol leads rapid construction synthetically versatile 2-methylquinoline derivatives (43 examples) excellent functionality tolerance.