Akichika Itoh

Molecular Iodine Catalyzed Cross-Dehydrogenative Coupling Reaction between Two sp3 C–H Bonds Using Hydrogen Peroxide

A useful method for molecular iodine catalyzed oxidative C-C bond formation between tertiary amines and a carbon nucleophile using hydrogen peroxide as the terminal oxidant is reported. This is the first report of a molecular iodine catalyzed cross-dehydrogenative coupling (CDC) reaction between two sp(3) C-H bonds.

Direct asymmetric aldol reaction with recyclable fluorous organocatalyst.

Direct asymmetric aldol reactions of aldehydes with ketones in the presence of a catalytic amount of fluorous sulfonamide 4 and trifluoroacetic acid result in the corresponding aldol products in high yields with up to 96% ee. The fluorous organocatalyst 4 can be readily recovered from the reaction mixture by fluorous solid-phase extraction and could be reused without a significant loss of the catalytic activity and enantioselectivity.

Direct Aerobic Photo-Oxidative Synthesis of Aromatic Methyl Esters from Methyl Aromatics via Dimethyl Acetals

A useful method for facile synthesis of aromatic methyl esters from methyl aromatics via dimethyl acetals by aerobic photo-oxidation using inexpensive and easily handled CBr(4) as catalyst is reported. This is the first example for direct preparation of the corresponding aromatic methyl esters from methyl aromatics.

Molecular-iodine-catalyzed aerobic oxidative synthesis of β-hydroxy sulfones from alkenes

The synthesis of β-hydroxy sulfones from alkenes and sodium sulfinates under aerobic oxidative conditions was achieved in the presence of a catalytic amount of molecular iodine. Molecular oxygen in air serves as the terminal oxidant and the catalytic amount of molecular iodine acts as the sulfonyl radical initiator and peroxide reductant.

Facile aerobic photooxidation of methyl group in the aromatic nucleus in the presence of an organocatalyst under VIS irradiation

We report a useful method for a facile synthesis of carboxylic acids from methyl aromatics by aerobic photooxidation using VIS irradiation and easily handled 2-chloroanthraquinone as organic catalysts under mild conditions such as an air atmosphere and ambient pressure and temperature. This is a more environmentally benign oxidation than previous methods, which require drastic reaction conditions.

Enantiodivergent Synthesis of Both Enantiomeric Forms of Substituted Paraconic Acids Starting from D-Mannitol as a Chiral Pool.

Abstract Acetamide-acetal Claisen rearrangement of the C 2 -symmetric enediol easily derived from d -mannitol provided a chiral C8-building block, which was demonstrated to be versatile for divergent synthesis of both enantiomeric forms of substituted paraconic acids.

Tandem oxidation/rearrangement of beta-ketoesters to tartronic esters with molecular oxygen catalyzed by calcium iodide under visible light irradiation with fluorescent lamp.

It was found that beta-ketoesters were directly transformed to the corresponding alpha-hydroxymalonic esters, tartronic esters, with molecular oxygen catalyzed by calcium iodide under visible light irradiation from fluorescent lamp. This reaction includes tandem oxidation/rearrangement and has received much attention from the viewpoint of reduction of energy consumption, labor, and solvents.

Aerobic oxidation of alcohols under visible light irradiation of fluorescent lamp

A catalytic amount of magnesium bromide diethyl etherate enables us to carry out the aerobic photo-oxidation of alcohols under irradiation of VIS from a general-purpose fluorescent lamp. Aliphatic primary alcohols, secondary alcohols and benzyl alcohols generally afforded the carboxylic acids directly in good to high yield. The bromine radical is thought to be generated in situ by continuous aerobic photo-oxidation of the bromo anion from MgBr2·Et2O, and to effect this oxidation reaction.

Selective acceleration for deprotection of benzyl ethers with Ti-HMS

Abstract Ti-HMS, a Ti-loaded hexagonal mesoporous silica, was found to accelerate deprotection of benzyl ethers under hydrogenolytic conditions with palladium catalyst. Such acid-sensitive functional groups as silyl ether and acetal moieties in the molecule were little affected by Ti-HMS, which possesses Lewis acid sites due to Ti-atom.

One-pot metal-free syntheses of acetophenones from styrenes through aerobic photo-oxidation and deiodination with iodine.

A one-pot synthetic protocol of acetophenones from styrenes with molecular oxygen, visible light, and molecular iodine is reported. This procedure involves aerobic photo-oxidation and deiodination in one pot and provides the first report of metal-free direct syntheses of acetophenones from styrenes.