Development of a high-performance liquid chromatographic glycated albumin assay using finger-prick blood samples.

Background: Home blood glucose monitoring can be effective for the self-management of diabetic patients. Hemoglobin A1c (HbA1c) is a widely used marker that reflects the average blood glucose within 1-2 months but does not sensitively respond to behavioral changes. Self-monitoring of blood glucose, continuous glucose monitoring, and flush glucose monitoring are sensitive; however, the cost and invasiveness of these tests prevent their widespread use.

5-Position-selective C-H trifluoromethylation of 8-aminoquinoline derivatives.

We developed a copper-catalyzed 5-position-selective C-H trifluoromethylation of 8-aminoquinoline derivatives. The reaction proceeded with high functional group tolerance under mild conditions. In the case of quinolines with an amide, carbamate, urea, or sulfonamide group at the 8-position of quinoline moieties, a radical scavenger experiment indicated that the reaction proceeded via a radical pathway.

A meta-selective C-H borylation directed by a secondary interaction between ligand and substrate.

Regioselective C-H bond transformations are potentially the most efficient method for the synthesis of organic molecules. However, the presence of many C-H bonds in organic molecules and the high activation barrier for these reactions make these transformations difficult. Directing groups in the reaction substrate are often used to control regioselectivity, which has been especially successful for the ortho-selective functionalization of aromatic substrates.

Rhenium-catalyzed regio- and stereoselective synthesis of γ-thio-α,β-unsaturated ketones via insertion of terminal alkynes into the C-S bond.

The reaction of α-thioketones and alkynes in the presence of a rhenium catalyst, [HRe(CO)(4)](n), gave γ-thio-α,β-unsaturated ketones in excellent yields. The alkynes were inserted into the carbon-sulfur bond of the α-thioketones, and isomerization of a double bond provided the products with high regio- and stereoselectivities. This reaction also proceeded in an intramolecular fashion.

Rhenium-catalyzed regio- and stereoselective addition of two carbon units to terminal alkynes via carbon-carbon bond cleavage of β-keto sulfones.

Treatment of β-keto sulfones with terminal alkynes gave unsaturated δ-keto sulfones in good to excellent yields under rhenium catalysis. In this reaction, the insertion of the alkynes into the nonstrained carbon-carbon single bond between the α- and β-positions of the β-keto sulfones proceeded smoothly, and (Z)-isomers were produced with high regio- and stereoselectivities.

Iron-catalyzed synthesis of glycine derivatives via carbon-nitrogen bond cleavage using diazoacetate.

Treatment of tertiary amines with diazoacetate in the presence of a catalytic amount of an iron salt, FeCl(3), in ethanol gave glycine derivatives. In this reaction, a carbon-nitrogen single bond of the amine was cleaved.

Rhenium- and manganese-catalyzed synthesis of aromatic compounds from 1,3-dicarbonyl compounds and alkynes.

We have succeeded in the development of three approaches to the synthesis of aromatic compounds from 1,3-dicarbonyl compounds and alkynes. The first approach is a manganese-catalyzed [2+2+2] cycloaddition between 1,3-dicarbonyl compounds, which have no substituents at the active methylene moiety, and terminal alkynes. This reaction proceeds with high regioselectivity when aryl acetylenes are employed as the alkyne component.

Rhenium- and manganese-catalyzed insertion of alkynes into a carbon-carbon single bond of cyclic and acyclic 1,3-dicarbonyl compounds.

Treatment of alkynes with cyclic and acyclic 1,3-dicarbonyl compounds in the presence of a catalytic amount of a rhenium or manganese complex gives ring-expanded and carbon-chain extension products, respectively. In these reactions, alkynes insert into a non-strained carbon-carbon single bond of 1,3-dicarbonyl compounds. The ring-expansion reaction is also promoted by the addition of 4-A molecular sieves instead of a catalytic amount of an isocyanide.

Rhenium-catalyzed formation of bicyclo[3.3.1]nonene frameworks by a reaction of cyclic beta-keto esters with terminal alkynes.

Treatment of cyclic beta-keto esters with terminal alkynes in the presence of a catalytic amount of a rhenium complex, [ReBr(CO)(3)(thf)](2), gave bicyclo[3.3.1]nonene derivatives.

Rhenium- and manganese-catalyzed insertion of acetylenes into beta-keto esters: synthesis of 2-pyranones.

Rhenium- and manganese-catalyzed reactions between beta-keto esters and acetylenes, followed by treatment with tetrabutylammonium fluoride, gave 2-pyranone derivatives regioselectively.

Manganese-catalyzed construction of tetrasubstituted benzenes from 1,3-dicarbonyl compounds and terminal acetylenes.

Treatment of beta-keto esters with terminal acetylenes in the presence of a catalytic amount of a manganese complex, MnBr(CO)5, and molecular sieves, gave multisubstituted aromatic compounds in good to excellent yields. This reaction employs [2 + 2 + 2] cycloaddition of beta-keto esters and 2 equiv of terminal acetylenes with dehydration. In the case of a 1,3-diketone, the corresponding acetophenone derivative and its deacylated compound can be synthesized selectively.