8-Iodoisoquinolinone, a Conformationally Rigid Highly Reactive 2-Iodobenzamide Catalyst for the Oxidation of Alcohols by Hypervalent Iodine.

The first lactam-type 2-iodobenzamide catalysts, 8-iodoisoquinolinones 8 (IB-lactam) and 9 (MeO-IB-lactam), were developed. These catalysts have a conformationally rigid 6/6 bicyclic lactam structure and are more reactive than the previously reported catalysts 2-iodobenzamides 4 (IBamide) and 5 (MeO-IBamide) for the oxidation of alcohols. The lactam structure could form an efficient intramolecular I---O interaction, depending on the size of the lactam ring.

Efficient and Environmentally Benign Oxidative Cleavage of Pyrrolidine-2-methanols to γ-Lactams Using 2-Iodobenzamide as a Catalyst and Oxone.

The oxidative cleavage reaction of pyrrolidine-2-methanols to γ-lactams has been described. In this reaction, [4-iodo-3-(isopropylcarbamoyl)phenoxy]acetic acid and powdered Oxone (2KHSO5·KHSO4·K2SO4) were employed as the catalyst and co-oxidant, respectively. The reaction is efficient and environmentally benign because it produces various lactams from readily available substrates in moderate to excellent yields using organocatalyst and inorganic non-toxic co-oxidant.

Bismuth(III)-Catalyzed Oxidative Cross-Coupling of 3-Hydroxycarbazoles with Arenols under an Oxygen Atmosphere.

A Bi(OTf)3-catalyzed oxidative cross-coupling reaction of 3-hydroxycarbazoles with arenols was developed under mild conditions. Both substrates were used in a 1:1 molar ratio in the presence of a catalytic amount of Bi(OTf)3. The reaction was carried out under an oxygen atmosphere at 30 °C to afford C1-symmetric hydroxybiaryls in good yields (up to 94%) with high chemo- and regioselectivity.

Lipase-Catalyzed Kinetic Resolution of C1-Symmetric Heterocyclic Biaryls.

The highly enantioselective lipase-catalyzed kinetic resolution (KR) of racemic C1-symmetric biaryl compounds including heterocyclic moieties, such as carbazole and dibenzofuran, has been achieved for the first time. This enzymatic esterification was accelerated by the addition of disodium carbonate while maintaining its high enantioselectivities, and was particularly effective for biaryls having N-substituted carbazole moieties. Furthermore, mesoporous silica-supported oxovanadium-catalyzed cross-dehydrogenative coupling of 3-hydroxycarbazole and 2-naphthol was followed by the lipase-catalyzed KR in one-pot to synthesize the optically active heterocyclic biaryl compounds with high optical purity.

Chemo- and regioselective cross-dehydrogenative coupling reaction of 3-hydroxycarbazoles with arenols catalyzed by a mesoporous silica-supported oxovanadium.

Cross-dehydrogenative coupling between 3-hydroxycarbazoles and 2-naphthols has been achieved by using a mesoporous silica-supported oxovanadium catalyst.

Base-promoted lipase-catalyzed kinetic resolution of atropisomeric 1,1'-biaryl-2,2'-diols.

Herein we report a dramatic acceleration of the lipase-catalyzed kinetic resolution of atropisomeric 1,1'-biaryl-2,2'-diols by the addition of sodium carbonate. This result likely originates from the increased nucleophilicity of the phenolic hydroxyl group toward the acyl-enzyme intermediate. Under these conditions, various substituted C 2-symmetric and non-C 2-symmetric binaphthols and biphenols were efficiently resolved with ∼50% conversion in only 13-30 h with excellent enantioselectivity.