Rhodium-catalyzed NH insertion of pyridyl carbenes derived from pyridotriazoles: a general and efficient approach to 2-picolylamines and imidazo[1,5-a]pyridines.

A general and efficient NH insertion reaction of rhodium pyridyl carbenes derived from pyridotriazoles was developed. Various NH-containing compounds, including amides, anilines, enamines, and aliphatic amines, smoothly underwent the NH insertion reaction to afford 2-picolylamine derivatives. The developed transformation was further utilized in a facile one-pot synthesis of imidazo[1,5-a]pyridines.

A new reactivity mode for the diazo group: diastereoselective 1,3-aminoalkylation reaction of β-amino-α-diazoesters to give triazolines.

A novel mode of reactivity for the diazo group, the 1,3-addition of a nucleophile and an electrophile to the diazo group, has been realized in the intramolecular aminoalkylation of β-amino-α-diazoesters to form tetrasubstituted 1,2,3-triazolines. The reaction exhibited a broad scope, good functional group tolerance, and excellent diastereoselectivity. In addition, a new Au-catalyzed intramolecular transannulation reaction of the obtained propargyl triazolines to give pyrroles has been discovered.

Conversion of 1-alkenes into 1,4-diols through an auxiliary-mediated formal homoallylic C-H oxidation.

The ubiquitous nature of C-H bonds in organic molecules makes them attractive as a target for rapid complexity generation, but brings with it the problem of achieving selective reactions. In developing new methodologies for C-H functionalization, alkenes are an attractive starting material because of their abundance and low cost. Here we describe the conversion of 1-alkenes into 1,4-diols.

General and practical carboxyl-group-directed remote C-H oxygenation reactions of arenes.

for remote aromatic C–H oxygenation reaction have been developed. Method 1, the Cu-catalyzed oxygenation reaction is highly efficient for cyclization of electron-neutral and electron-rich biaryl carboxylic acids into 3,4-benzocoumarins. Method 2, the KSO-mediated oxygenation reaction, is more general and practical for cyclization of substrates with electron- donating and -withdrawing groups (see scheme).

Twofold unsymmetrical C-H functionalization of PyrDipSi-substituted arenes: a general method for the synthesis of substituted meta-halophenols.

Two-fold unsymmetrical functionalization of arenes, which includes sequential halogenation/oxygenation reactions, has been developed. This transformation allows for a general and efficient synthesis of substituted -halophenols from simple aryl iodides. Importantly, the PyrDipSi (2-diisopropylsilylpyrimidine) group can be easily removed or efficiently converted into valuable functionalities.

Pyridine group assisted addition of diazo-compounds to imines in the 3-CC reaction of 2-aminopyridines, aldehydes, and diazo-compounds.

A novel three-component coupling (3-CC) reaction of 2-aminoazines, aromatic aldehydes, and diazo-compounds producing polyfunctional β-amino-α-diazo-compounds has been developed. The reaction features an unprecedented heterocycle-assisted addition of a diazo-compound to an imine. The obtained diazoesters were efficiently converted into valuable heterocycles as well as β-amino acid derivatives.

Double-fold C-H oxygenation of arenes using PyrDipSi: a general and efficient traceless/modifiable silicon-tethered directing group.

The efficient Pd-catalyzed double-fold C-H oxygenation of arenes into resorcinols using the newly developed 2-pyrimidyldiisopropylsilyl (PyrDipSi) directing group is described. Its use allows for the sequential introduction of OAc and OPiv groups in a one-pot manner to produce orthogonally protected resorcinol derivatives. The PyrDipSi group is superior to the previously developed 2-pyridyldiisopropylsilyl (PyDipSi) group, as it is efficient for monooxygenation of ortho-substituted arenes.

Multicomponent synthesis of artificial nucleases and their RNase and DNase activity.

The synthesis of new, artificial ribonucleases containing two amino acid residues connected by an aliphatic linker has been developed. Target molecules were synthesized via a catalytic three-component Ugi reaction from aliphatic diisocyanides. Preliminary investigations proved unspecific nuclease activity of the new compounds towards single-stranded RNA and double-stranded circular DNA.

The first example of a diastereoselective thio-Ugi reaction: a new synthetic approach to chiral imidazole derivatives.

The first example of a diastereoselective thio-Ugi reaction with chiral alpha-methylbenzylamine is described. The reaction results in formation of two diastereomers of thioamides, the major of which was isolated. We have found that under similar conditions stereochemical results of the thio-Ugi reaction are opposite to stereochemical results of the Ugi reaction.