Fluorogenic sydnonimine probes for orthogonal labeling.

A FRET-based fluorescence turn-on probe is designed, which employs a sydnonimine as the linker to match specific fluorophore and quencher pairs and releases the fluorescence after the "click-and-release" reaction. Furthermore, we realized selective fluorescence labeling by exploiting the mutual orthogonality between sydnonimine-DIBAC and tetrazine-1,3-Cp cycloaddition pairs.

Bioorthogonal release of sulfonamides and mutually orthogonal liberation of two drugs.

Sulfonamide derivatives have been used in pharmaceutics for decades. Here we report a new approach to release sulfonamides efficiently using a bioorthogonal reaction of sulfonyl sydnonimines and dibenzoazacyclooctyne (DIBAC). The second-order rate constant of the cycloaddition reaction can be up to 0.

Origins of halogen effects in bioorthogonal sydnone cycloadditions.

Halogen substituents increase sydnone cycloaddition reactivities substantially. Fluoro-sydnones are superior to bromo- and chloro-sydnones, and can achieve extremely high second-order rate constants with strained alkynes. Computational studies have revealed the fluorine substituent increases the reactivity of sydnone mainly by lowering its distortion energy.

Catalyst-free tandem Michael addition/decarboxylation of (thio)coumarin-3-carboxylic acids with indoles: facile synthesis of indole-3-substituted 3,4-dihydro(thio)coumarins.

The tandem Michael addition/decarboxylation of (thio)coumarin-3-carboxylic acids with indoles has been developed and the biologically important indole-3-substituted dihydrocoumarins were obtained in good to excellent yields under catalyst-free conditions.

Tandem sp3 C-H functionlization/decarboxylation of 2-alkylazaarenes with coumarin-3-carboxylic acids.

The catalyst-free sp(3) C-H functionalization of 2-alkylazaarenes has been achieved in the reaction with (thio)coumarin-3-carboxylic acids. Followed by a tandem decarboxylation, this method provides facile synthesis of biologically important azaarene-substituted 3,4-dihydro(thio)coumarins in a single step in high yields.