On-DNA-1,2,3-Triazole Formation via Click Reaction.

Copper-catalyzed azide-alkyne cycloaddition (CuAAC) provides a simple and convenient strategy to synthesize diverse 1,2,3-triazoles for drug discovery. Described herein is a protocol for the CuSO-catalyzed cycloaddition between alkynes and DNA-appended azides.

Selective ring-rearrangement or ring-closing metathesis of bicyclo[3.2.1]octenes.

Explored was the competitive ring-closing metathesis vs. ring-rearrangement metathesis of bicyclo[3.2.

Controlling, Understanding, and Redirecting the Thermal Rearrangement of 3,3-Dicyano-1,5-enynes.

The thermal [3,3] rearrangement of 3,3-dicyano-1,5-enynes to γ-allenyl alkylidenemalononitriles (the "enyne Cope rearrangement") has largely eluded synthetic value as the desired products, too, are thermally reactive and ultimately yield 6π electrocyclization products. Herein, we describe experimental and computational studies related to the thermal rearrangement of 1,5-enynes, structural features to halt the thermal rearrangement at the allene stage, and a reductive variant for preparing bifunctional allenyl malononitriles. We also describe various ways that the bifunctional building blocks can be manipulated and converted to cyclic and acyclic architectures.

An Enyne Cope Rearrangement Enables Polycycloalkane Synthesis from Readily Available Starting Materials.

Cyclohexanone-derived Knoevenagel adducts (cyclohexylidenemalononitriles) and two different propargyl electrophiles serve as carbon sources for assembling diverse 6/7/5 tricycloalkanes, a common terpenoid framework. The sequence involves three unique reactions: 1) deconjugative propargylation, 2) one-pot enyne Cope rearrangement/deconjugative propargylation, and 3) an allenic Pauson-Khand reaction.