The room-temperature oxidative C–H/C–H cross-couplings between simple arenes and alkenes, coumarins or quinones have been reported by using a highly electrophilic palladium species [Pd(TFA)₂] as the catalyst cheap (NH₄)₂S₂O₈ oxidant under air.

The installation of (benzo)thiophene-containing biaryls via coupling reactions has become a staple in designing photoelectric materials. Undeniably, C–H/C–H cross-coupling between two (hetero)aromatics would be shortcut toward these structural fragments. While more reliable technologies are well-established to provide C2-arylated (benzo)thiophenes, efficient methods that arylate the C3-position remain underdeveloped. Herein we insight into factors determine regioselectivity switching for...

By making use of a dual-chelation-assisted strategy, completely regiocontrolled oxidative C-H/C-H cross-coupling reaction between an N-acylaniline and benzamide has been accomplished for the first time. This process constitutes step-economic highly efficient pathway to 2-amino-2'-carboxybiaryl scaffolds from readily available substrates. A Cp*-free RhCl3 /TFA catalytic system was developed replace [Cp*RhCl2 ]2 /AgSbF6 generally used in reactions two (hetero)arenes...

Abstract The hydroformylation of alkynes is a fundamental and important reaction in both academic research industry. Conventional methods focus on the conversion alkynes, CO, H 2 into α,β‐unsaturated aldehydes, but they often suffer from problems associated with operation, regioselectivity, chemoselectivity. Herein, we disclose an operationally simple, mild, syngas‐free rhodium‐catalyzed for via formyl hydride transfer alkyl aldehyde. This synthetic method uses inexpensive easy‐to‐handle n...

Herein we disclose the first example of transition-metal-catalyzed oxidative coupling/annulation simple benzoic acids with terminal alkynes via C–H activation. A range aromatic carboxylic and have been found to be viable substrates in this reaction, providing a efficient method for synthesis diverse 3-ylidenephthalides complete Z selectivity.

β-Azolyl propanoic acid derivatives are frequently found in biologically active molecules and pharmaceuticals. Here, we report the oxidative heteroarylation of unactivated C(sp3)-H bonds with azole C(sp2)-H via copper or nickel catalysis aid removable bidentate auxiliary, which provides a rapid pathway to β-azolyl derivatives. A variety azoles such as oxazole, benzoxazole, thiazole, benzothiazoles, benzimidazole, purine, even [1,2,4]triazolo[1,5-a]pyrimidine could be engaged this protocol.

An urgent yet challenging task is to overcome the limitations in substrate scope and regio- chemoselectivity oxidative couplings between two arenes for construction of unsymmetrical 2,2′-difunctional biaryls with diverse application requirements. In this work, a co-oxidant-free Rh(I)/Zn(NTf2)2/air catalytic system has been developed dual chelation-assisted C–H/C–H cross-couplings anilines, phenols, phenols which enables rapid assembly rich libraries 2,2′-bianilines, 2,2′-biphenols,...

In this work, we report novel Rh(iii)-catalyzed chemoselective functionalizations of tertiary aniline N-oxides with alkynes, including annulation via the sequential C(sp(2))-H and C(sp(3))-N activation for formation N-alkylindoles an O-atom transfer (OAT) process synthesis acetophenones.

Described herein is a dual chelation-assisted RhCl₃-catalyzed oxidative C–H/C–H cross-coupling reaction of aniline derivatives, in which the chemo- and regioselective between electronically similar substrates achieved.

The development of a strategy for remote C7–H functionalizations the naphthalene rings is greatly challenging. Disclosed herein an example direct and regioselective arylation at C7 position that promoted by F+ reagents. This protocol features good tolerance reactive functional groups, mild reaction conditions, simple system. By control experiments, kinetic isotope effect (KIE) experiment, NMR mechanistic pathway involving carbopalladation/aryl migration has been illustrated clearly. Beyond...

The O-site reactivity of difluoroenoxysilanes is disclosed for the first time, which enabled direct construction versatile gem-difluoroalkenes through an unprecedented highly efficient addition reaction with ketenes. A series valuable gem-difluoroenol esters were achieved in good to excellent yields. synthetic versatility this protocol further demonstrated by gram-scale synthesis and functional group tolerance.

4-Fluoro-2-methoxy-5-nitrophenol is a key intermediate of the GnRH receptor antagonist Linzagolix. The traditional synthetic methods have several disadvantages including prolonged reaction time and safety issues. Herein, we describe three-step continuous flow synthesis 4-fluoro-2-methoxy-5-nitrophenol via esterification, nitration, hydrolysis. total residence was 234 s, yield 85.6%, which substantially reduced considerably improved process as well yield.

Abstract The first allylic alkylation of difluoroenoxysilanes with MBH carbonates catalyzed by triethylenediamine (DABCO) is developed, which allows rapid access to multifunctional α ‐ gem ‐difluoroketones up 97% yields. Moreover, the gram‐scale synthesis and diversifying transformation products valuable ‐difluorinated molecules highlight practicality this methodology.

Abstract The hydroformylation of alkynes is a fundamental and important reaction in both academic research industry. Conventional methods focus on the conversion alkynes, CO, H 2 into α,β‐unsaturated aldehydes, but they often suffer from problems associated with operation, regioselectivity, chemoselectivity. Herein, we disclose an operationally simple, mild, syngas‐free rhodium‐catalyzed for via formyl hydride transfer alkyl aldehyde. This synthetic method uses inexpensive easy‐to‐handle n...

Abstract By making use of a dual‐chelation‐assisted strategy, completely regiocontrolled oxidative C−H/C−H cross‐coupling reaction between an N ‐acylaniline and benzamide has been accomplished for the first time. This process constitutes step‐economic highly efficient pathway to 2‐amino‐2′‐carboxybiaryl scaffolds from readily available substrates. A Cp*‐free RhCl 3 /TFA catalytic system was developed replace [Cp*RhCl 2 ] /AgSbF 6 generally used in reactions two (hetero)arenes...

Abstract 1,3‐Dipolar cycloaddition of isatin N,N′ ‐cyclic azomethine imine catalyzed by CuCO 3 has been developed. Structurally interesting heterocyclic spiro(indoline‐3,1′‐pyrazolo[1,2‐ a ]pyrazoles) have synthesized as single regioisomers in good yields and high functional group compatibility.

We present a novel highly stereoselective Rh-catalyzed cyclopropanation of diazothiooxindoles with broad range α-functionalized styrenes, enabling facile access chiral spirocyclopropylthiooxindoles in high to excellent enantiomeric excess.

Transition-metal-catalyzed directed C-H allylation of arenes offers an efficient and straightforward approach to construct value-added allylic arenes. However, these reactions are often performed with precious transition-metal catalysts mainly limited ortho-C-H Herein, we disclose a novel iron-catalyzed para-C-H aniline derivatives allyl alcohols via chelation-induced strategy, providing various in good yields excellent regio- chemoselectivity. A simple FeCl3·6H2O is employed as catalyst,...

In this reaction, a new strategy for the synthesis of indoles from<italic>N</italic>-(<italic>ortho</italic>-chloromethyl)aryl carbamates and terminal alkynes<italic>via</italic>Cu-catalyzed coupling–cyclization has been developed.