The remarkable solvent effect on Zn(OAc)2-catalyzed hydrosilylation of ketones.

The combination of Zn(OAc)(2) and N,N-dimethylformamide was found to effectively hydrosilylate various ketones at room temperature. Furthermore, our protocol allows the chemoselective reduction of a formyl group in the presence of a ketone group.

Facile two-step synthesis of 3-substituted indazoles using diazo(trimethylsilyl)methylmagnesium bromide.

Diazo(trimethylsilyl)methylmagnesium bromide readily reacted with various ketones and aldehydes to give the corresponding 2-diazo-(2-trimethylsilyl)ethanols. These were efficiently converted to indazoles bearing hydroxymethyl units at the 3-position by intermolecular [3 + 2] cycloaddition with benzynes.

Interesting nickel-catalyzed 1,2-addition to alpha,beta-unsaturated aldehydes with arylborates.

Ni-Et-Duphos-catalyzed 1,2-addition of potassium aryltrifluoroborates to alpha,beta-unsaturated aldehydes is described.

Development of novel hemilabile Segphos P-P=O ligands.

Development of novel chiral hemilabile Segphos P-P=O ligands is described. The ligands are examined for enantioselective Pd-catalyzed allylic alkylation of cyclic allylic acetates.

Asymmetric construction of quaternary carbon stereocenter by Pd-catalyzed intramolecular alpha-arylation.

The catalyst comprised of Pd(OAc)(2) and H(8)-BINAP provides good reaction conversions for a catalytic enantioselective intramolecular alpha-arylation of N-(2-bromophenyl)-N-methyl-2-arylpropanamide to form the quaternary carbon with up to 68% enantioselectivity.

Function of an N-heterocyclic carbene ligand based on concept of chiral mimetic.

Function of a new N-heterocyclic carbene ligand based on the concept of a chiral mimetic is described. With (4R,5R)-4,5-diphenyl-1,3-dialkyl-4,5-dihydro-3H-imidazol-1-ium tetrafluoroborates as N-heterocyclic carbene precursors, Rh-catalyzed enantioselective arylation (up to 27% ee) of aromatic aldehydes with arylboronic acids and Pd-catalyzed enantioselective intramolecular alpha-arylation (up to 66% ee) of N-(2-bromoaryl)-N-alkyl-2-arylpropanamides are investigated.

Cyano-phosphorylation of aldehydes catalyzed by a nucleophilic N-heterocyclic carbene.

The first method for cyano-phosphorylation of aldehydes with diethyl cyanophosphonate in the presence of N-heterocyclic carbene prepared from 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride and KOt-Bu, as a nucleophilic catalyst, is described.

Asymmetric Michael reaction promoted by new chiral phase-transfer catalysts.

A catalytic asymmetric Michael reaction promoted by new chiral quaternary ammonium salts is described. The products are obtained with moderate ee (up to 75% ee), and the enantioselectivity is strongly dependent on both the substituents on the aromatic rings and the ammonium moiety in the catalysts.