1454880-68-2

Upstream product

• 1454880-62-6 N-(1-(2,5-cimethylphenyl)naphthalen-2-yl)methanesulfonamide 
• 106-42-3 para-xylene 
• 3989-47-7 N-(naphthalen-2-yl)methanesulfonamide 
• 20191-75-7 1-bromo-2-naphthylamine 
• 85199-06-0 2,5-dimethylphenyl boronic acid 
• 90016-93-6 2-Amino-1-iodonaphthalene 

Relevant academic research and scientific papers

Enhanced Reactivity by Torsional Strain of Cyclic Diaryliodonium in Cu-Catalyzed Enantioselective Ring-Opening Reaction

Atropisomers are stereoisomers arising from the restricted rotation around a single bond. In particular, biaryl atropisomers represent an important class of compounds, as they are widely present in natural products, ligands and pharmaceutical molecules. However, the preparation of structurally diverse biaryl atropisomers under mild conditions is a significant challenge. Here, we describe a Cu-bis(oxazolinyl)pyridine-catalyzed asymmetric ring-opening amination reaction of cyclic diaryliodoniums. Increasing the torsional strain of these cyclic compounds significantly improved the reactivity of cyclic diaryliodoniums. Computational investigation indicated that the two conformers of the cyclic diaryliodoniums had a low rotational barrier, and generally the reaction achieved high yields and high enantioselectivity (up to >99% ee). Furthermore, this ring-opening amination reaction also featured high atom economy in comparison with traditional reactions involving diaryliodonium. Finally, we propose a catalytic cycle and a mechanistic model that accounts for the observed enantioselectivity. Axially chiral biaryls represent an important class of stereoisomers that arise from restricted rotation around a single bond. They can be found among natural products, ligands, and pharmaceutical molecules. Divergent and atom-economic synthetic approaches toward optically active biaryl atropisomers, in particular ones generating little to no waste, constitute a significant challenge. Here, we describe a highly enantioselective copper-catalyzed ring-opening reaction of cyclic diaryliodoniums where increasing the torsional strain of the diaryliodonium salts improved the relative poor reactivity of the cyclic diaryliodoniums. This method enabled us to access enantio-enriched amino aryliodides with higher atom economy than traditional reactions involving diaryliodonium. These axially chiral molecules are important precursors for divergent synthesis of axially chiral compounds, which are potentially useful catalysts or ligands in industry. An efficient method is developed for preparing functionalized axially chiral compounds via the ring-opening reaction of cyclic diaryliodonium salts. Two conformers of the cyclic diaryliodonium salt observed in the crystal structure underwent quick equilibration. The distortion of the diaryliodonium salts significantly increased reactivity toward the chiral copper catalyst, which enabled the reaction to take place in mild conditions to furnish the products in enantioselectivities up to 99.5:0.5 (R:S).

Copper-Catalyzed Asymmetric Ring-Opening of Cyclic Diaryliodonium with Benzylic and Aliphatic Amines

A Cu-catalyzed asymmetric ring-opening reaction between cyclic diaryliodonium and benzylic or aliphatic amines has been developed. At low concentration of the amines, realized by either mixing the amines with Lewis acid or slow addition of the amines, the reaction afforded the products in high enantioselectivity. (Figure presented.).

Hexafluoroisopropanol-Enabled Copper-Catalyzed Asymmetric Halogenation of Cyclic Diaryliodoniums for the Synthesis of Axially Chiral 2,2′-Dihalobiaryls

An efficient asymmetric halogenation of cyclic diaryliodonium salts is demonstrated, which gives access to a wide range of axially chiral 2,2′-dihalobiaryls in good to excellent yields and with excellent enantioselectivities. The use of CuX with chiral bisoxazoline ligand and tetrabutylammonium halides in the unique solvent of hexafluoroisopropanol (HFIP) led to the best results in the process. The axially chiral 2,2′-dihalobiaryls can be transformed into a number of enantiopure chiral ligands that could be potentially useful in asymmetric catalysis.

Organocatalytic C-H/C-H' cross-biaryl coupling: C-selective arylation of sulfonanilides with aromatic hydrocarbons

The hypervalent iodine-mediated C-C selective coupling of N-methanesulfonyl anilides with aromatic hydrocarbons has been developed. The first organocatalytic oxidative cross-biaryl-coupling was achieved by the catalyst control in defining specific 2,2′-diiodobiphenyls for the direct C-C bond formations.