An efficient rhodium-catalyzed method for direct C-H functionalization at the C7 position of a wide range indoles has been developed. Good to excellent yields alkenylation products were observed with acrylates, styrenes, and vinyl phenyl sulfones, whereas saturated alkylation obtained in good yield α,β-unsaturated ketones. Both N-pivaloyl directing group rhodium catalyst proved be crucial high regioselectivity conversion.

CuI/4-hydroxy-l-proline catalyzed coupling of N-substituted o-bromobenzamides with formamide takes place at 80 °C, affording 3-substituted quinazolinones directly. Under these conditions other amides that were tested only provided simple products, which can be converted into 2,3-disubstituted via HMDS/ZnCl2 mediated condensative cyclization.

CuI/6-hydroxy picolinohydrazide-catalyzed coupling of (hetero)aryl chlorides with anilines proceeded well at 100 °C to afford biaryl amines in a diverse manner, which represents the first example Cu-catalyzed under milder conditions. The same catalytic system could make bromides work room temperature, giving corresponding products an excellent reaction scope.

Direct C7-amination of N-pivaloylindoles has been achieved using a combination [Cp*IrCl2]2, AgNTf2, and AgOAc as the catalyst sulfonoazides nitrogen source. The reaction proceeded at room temperature to 80 °C afford 7-sulfonamidoindoles in good excellent yields. is broadly applicable wide variety 3-, 4-, 5-, 6-substituted with either alkyl or aryl sulfonoazides.

α-(Hetero)aryl nitriles are important structural motifs for pharmaceutical design. The known methods direct synthesis of these compounds via coupling with (hetero)aryl halides suffer from narrow reaction scope. Herein, we report that the combination copper salts and oxalic diamides enables a variety (Cl, Br) ethyl cyanoacetate under mild conditions, affording α-(hetero)arylacetonitriles one-pot decarboxylation. Additionally, CuBr/oxalic diamide catalyzed bromides α-alkyl-substituted...

Direct N-arylation of sulfonamides is a very attractive approach for preparing pharmaceutically important N-(hetero)aryl because it avoids the potential genotoxic problem resulting from previous condensation method. Most known catalytic methods suffer limited reaction scope and inconveniency on metal catalyst ligand availability. Here we described that combination copper oxalamides (or 4-hydroxypicolinamides) offers powerful system sulfonamides. A wide range primary secondary were able to...

Abstract An efficient rhodium‐catalyzed method for direct CH functionalization at the C7 position of a wide range indoles has been developed. Good to excellent yields alkenylation products were observed with acrylates, styrenes, and vinyl phenyl sulfones, whereas saturated alkylation obtained in good yield α,β‐unsaturated ketones. Both N ‐pivaloyl directing group rhodium catalyst proved be crucial high regioselectivity conversion.

A short and efficient synthesis of (S)-N-Boc-2,6-dimethyltyrosine utilizing palladium-catalyzed directed C-H functionalization is described. This represents the first general method for ortho-dimethylation tyrosine derivatives offers a practical approach preparing this synthetically important building block. Notably, throughout reaction sequence no racemization occurs at susceptible α-chiral centers.

The (S)-nobin-embodied picolinamide and L-hydroxyproline-derived amide are effective ligands for Cu-catalyzed enantioselective coupling reaction of (hetero)aryl iodides with α-alkyl substituted cyanoacetates. This arylation gave α-(heteroaryl)-α-alkyl cyanoacetates in good to excellent enantioselectivities (up 95 % ee). A variety functionalized alkyl groups could be introduced the quaternary center therefore provided a valuable tool preparing enantioenriched compounds an all-carbon tethered...

Double amination of ortho-substituted aryl bromides proceeded under mild conditions to afford 5-substituted 11-oxo-dibenzodiazepines, which revealed that there is a strong ortho-substituent effect caused by N-aryl aminocarbonyl groups during copper-catalyzed amination.

CuBr-catalyzed coupling reaction of 2-halobenzonitriles with hydrazine carboxylic esters and CuBr/4-hydroxy-l-proline-catalyzed 2-bromobenzonitriles N'-arylbenzohydrazides proceed smoothly at 60-90 °C to provide substituted 3-aminoindazoles through a cascade coupling/condensation (or coupling/deacylation/condensation) process. A wide range substituents both the 1-position phenyl ring part can be prepared from corresponding partners.

Abstract An efficient rhodium‐catalyzed direct C−H amidation of N ‐nitrosoanilines with 1,4,2‐dioxazol‐5‐ones as amidating agents has been developed. This method featured mild reaction conditions, a wide substrate scope and satisfactory yields. Besides, the amidated products could be readily converted to pharmaceutically valuable 1,2‐disubstituted benzimidazoles via an HCl‐mediated deprotection/cyclization process in one pot.

A rhodium-catalyzed regioselective C-H olefination of indazole is described. This protocol relies on the use an efficient and removable N,N-diisopropylcarbamoyl directing group, which offers facile access to C7-olefinated indazoles with high regioselectivity, ample substrate scope broad functional group tolerance.

N1-(2,6-Dimethylphenyl)-N2-(pyridin-2-ylmethyl)oxalamide (DMPPO) was revealed to be a more effective ligand for copper-catalyzed coupling reaction of (hetero)aryl halides with 1-alkynes than previously reported ones. Only 3 mol % CuCl and DMPPO are required make the complete at 100 °C (for bromides) 80 iodides). Both alkyl substituted worked well under these conditions, leading formation internal alkynes in great diversity.

Coming full circle: CuI/L-proline-catalyzed coupling of substituted 3-iodoprop-2-en-1-ols and terminal alkynes followed by copper-mediated cycloisomerization produced furans in good yields. This method allows the assembly 2,3,4- 2,3,5-trisubstituted furans, as well 2,3,4,5-tetrasubstituted furans. Detailed facts importance to specialist readers are published ”Supporting Information”. Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted authors. Please...

Hydroxylated (hetero)arenes are privileged motifs in natural products, materials, small-molecule pharmaceuticals and serve as versatile intermediates synthetic organic chemistry. Herein, we report an efficient Cu(I)/6-hydroxy picolinohydrazide-catalyzed hydroxylation reaction of (hetero)aryl halides (Br, Cl) water. By establishing machine learning (ML) models, the design ligands optimization conditions were effectively accelerated. The N-(1,3-dimethyl-9H- carbazol-9-yl)-6-hydroxypicolinamide...

A CuCl catalyzed C-N cross-coupling reaction using commercially available 1H-indazoles with diaryliodonium salts is described. The methodology features ample structural versatility, affording 2-substituted-2H-indazole in good yields and complete N(2)-regiocontrol. Furthermore, the utility of was demonstrated synthesis a known estrogen receptor β agonist. Mechanistic studies density functional theory calculations suggested that regioselectivity can be attributed to only weak base TfO- our...

A highly efficient rhodium-catalyzed, solvent-controlled regioselective C–H halogenation of anilines by using <italic>N</italic>-nitroso as a suitable and removable directing group was achieved under mild reaction conditions.

Abstract Direct N ‐arylation of sulfonamides is a very attractive approach for preparing pharmaceutically important ‐(hetero)aryl because it avoids the potential genotoxic problem resulting from previous condensation method. Most known catalytic methods suffer limited reaction scope and inconveniency on metal catalyst ligand availability. Here we described that combination copper oxalamides (or 4‐hydroxypicolinamides) offers powerful system sulfonamides. A wide range primary secondary were...

A highly efficient and generally applicable protocol, starting from 2-bromobenzamides 2-bromo(thio)phenols via twice copper-catalyzed couplings to afford dibenzothiazepines dibenzoxazepinones has been developed. High levels of yield chemoselectivity are achieved in a single-pot reaction by using an appropriate ligand. Moreover, this facile methodology allows rapid access variety bio­active compounds known psychotropic drug, which should broaden its application organic synthesis.

Phosphonation of β-nitro-alkene with triethyl phosphite was achieved under microwave irradiation using CH2Cl2 as the solvent in absence catalyst moderate to high yields (up 90%). This method formation carbonphosphor bonds is simple, mild, convenient and effective. Synchronously, a number vinylphosphonates derivatives were synthesized evaluated biologically preliminary. Keywords: Vinylphosphonate, phosphonation, phosphite, B-nitro-alkene, irradiation, carbonphosphor, enantioselective,...

CuI-catalyzed coupling of 2-halotrifluoroacetanilides with l-proline or pipecolinic acid in DMSO at 90-110 ˚C followed by situ hydrolysis 100 afforded tetrahydropyrrolo[1,2-a]quinoxalines tetrahydropyrido[1,2-a]quinoxalines.

An efficient rhodium-catalyzed method for C–H olefination at the C7 position of indoles has been developed. The N-imino directing group was shown to be crucial high regioselectivity and reactivity metal catalyst. utility this protocol further demonstrated through a concise, four-step synthesis pyroquilon from indole.

Abstract α‐(Hetero)aryl nitriles are important structural motifs for pharmaceutical design. The known methods direct synthesis of these compounds via coupling with (hetero)aryl halides suffer from narrow reaction scope. Herein, we report that the combination copper salts and oxalic diamides enables a variety (Cl, Br) ethyl cyanoacetate under mild conditions, affording α‐(hetero)arylacetonitriles one‐pot decarboxylation. Additionally, CuBr/oxalic diamide catalyzed bromides α‐alkyl‐substituted...