26844-83-7

Upstream product

• 1679-18-1 4-Chlorophenylboronic acid 
• 615-36-1 2-bromoaniline 
• 124-38-9 carbon dioxide 
• 1204-44-0 2-(4-chlorophenyl)aniline 
• 615-43-0 2-iodophenylamine 
• 2446-83-5 di-isopropyl azodicarboxylate 
• 1609211-15-5 N-(4′-chloro-[1,1′-biphenyl]-2-yl)picolinamide 
• 6271-80-3 4'-chloro-2-nitrobiphenyl 
• 106-39-8 bromochlorobenzene 
• 190788-59-1 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)nitrobenzene 
• 27007-53-0 methyl-2-bromo-5-chlorobenzoate 
• 5570-18-3 2-aminophenylboronic acid 
• 201230-82-2 carbon monoxide 

Relevant academic research and scientific papers

Cu(0)/Selectfluor system-catalyzed intramolecular Csp2-H/Csp2-H cross-dehydrogenative coupling (CDC)

A Cu(0)/Selectfluor system-catalyzed intramolecular Csp2-H/Csp2-H bond cross-dehydrogenative coupling of 2-aryloxybenzaldehydes is described. A variety of substituted xanthone derivatives are synthesized in moderate to excellent yields. Reaction can also be extended to the synthesis of 9H-thioxanthen-9-one 10,10-dioxide and phenanthridin-6(5H)-ones, respectively.

Rhodium(I)-Catalyzed Aryl C-H Carboxylation of 2-Arylanilines with CO2

An unprecedented Rh(I)-catalyzed, amino-group-assisted C-H carboxylation of 2-arylanilines with CO2 under redox-neutral conditions has been developed. This reaction was promoted by a phosphine ligand with t-BuOK as the base and did not require the use of additional strong organometallic reagent. It enabled an efficient direct conversion of a broad range of 2-(hetero)arylanilines including electron-deficient heteroarenes to various phenanthridinones. Possible intermediates of the reaction were also evaluated in the preliminary mechanistic studies.

Preparation method of phenanthridone compounds

The invention provides a preparation method of phenanthridone compounds. The preparation method comprises the steps: dissolving a raw material, namely an N-o-aryl-formylaniline derivative I as shown in the formula I, into an organic solvent by taking a copper salt as a catalyst and a fluorine reagent as an oxidant, carrying out a reaction in a pressure-resistant sealed tube at 50-90 DEG C for 12-30h, and separating and purifying the obtained reaction liquid to prepare the phenanthridone compound as shown in the formula I. The synthesis method provided by the invention is simple in reaction step, good in substrate adaptability, high in atom economy, free of using expensive and poisonous catalysts or ligands in a reaction process, safe and environment-friendly, and all substituent groups canbe cyclized. The preparation method can be used for cyclizing oxidized C-H/C-H and is a novel method for synthesizing various phenanthridone compounds containing substituent groups.

Metal-Oxidant-Free Cobalt-Catalyzed C(sp2)-H Carbonylation of ortho-Arylanilines: An Approach toward Free (NH)-Phenanthridinones

A traceless directing group assisted Co-catalyzed C(sp2)-H carbonylation of ortho-arylanilines for the synthesis of free (NH)-phenanthridinones in metal-based-oxidant-free fashion was accomplished. This protocol employs diisopropyl azodicarboxylate as the CO source and oxygen as the sole oxidant, and provides good yields with various functional tolerance. The methodology has been applied for the total synthesis of PARP inhibitor PJ-34. Furthermore, the kinetic isotopic effect experiments reveal the C-H bond cleavage probably occurred in the rate-determining step.

MeOTf- and TBD-Mediated Carbonylation of ortho-Arylanilines with CO2 Leading to Phenanthridinones

Carbonylation of o-arylanilines utilizing CO2 as a carbonyl source for the synthesis of important phenanthridinones with a free (NH)-lactam motif has been described under metal-free condition. A range of o-arylanilines were transformed to the corresponding phenanthridinones in high yields.

Transition-metal-free synthesis of phenanthridinones from biaryl-2-oxamic acid under radical conditions

Na2S2O8-promoted decarboxylative cyclization of biaryl-2-oxamic acid for phenanthridinones has been developed. This work illustrates the first example of intramolecular decarboxylative amidation of unactivated arene under transition-metal-free conditions. Additionally, this approach provides an efficient and economical method to access biologically interesting phenanthridinones, an important structure motif in many natural products. (Chemical Equation Presented).

Pd(II)-catalyzed C(sp2)-H carbonylation of biaryl-2-amine: Synthesis of phenanthridinones

A Pd(OAc)2-catalyzed C(sp2)-H carbonylation protocol of arenes under carbon monoxide atmosphere has been developed. The scope of the carbonylation reaction is broad and tolerates a variety of useful functional groups. This reaction provides a novel and efficient method for the synthesis of biologically and pharmaceutically significant phenanthridinones.

A convenient one-pot access to phenanthridinones via Suzuki-Miyaura cross-coupling reaction

A convenient one-step access to biologically important phenanthridinones 1 has been realized based upon Suzuki-Miyaura cross-coupling reaction. Reactions of 2-aminophenylboronic acid 2 with 2-halobenzoate 3 took place smoothly to afford substituted phenanthridinones 1 in excellent yields in the presence of palladium(II) acetate and 2-dicyclohexylphosphino-2′,6′- dimethoxybiphenyl (SPhos) as pre-catalysts. A natural product phenaglydon 1b was synthesized in one-pot manner from readily available starting materials in 95% yield.

Synthesis of phenanthridinones via palladium-catalyzed C(sp2)-H aminocarbonylation of unprotected o-arylanilines

An efficient synthesis of free (NH)-phenanthridinones through Pd-catalyzed C(sp2)-H aminocarbonylation of unprotected o-arylanilines under an atmospheric pressure of CO has been developed. Some ortho heteroarene substituted anilines as well as