ABSTRACT
Copper-catalyzed carboazidation of alkenes with trimethylsilyl azide and cyclic ethers has been achieved. The employment of naturally abundant copper catalysts allowed cyclic ethers to be used as alkylating reagents under oxidative conditions. The use of styrene derivatives and 1,1-diaryl alkenes afforded carboazidation products. In addition, application of five- and six-membered cyclic ethers to the present reaction gave target organic molecules bearing azide and cyclic ether groups with perfect regioselectivity. Radical trapping and clock experiments revealed that the present reaction proceeded via the radical pathway. To further demonstrate the utility of this carboazidation reaction, transformations from the azide group to the related nitrogen-containing compounds were also performed.
ABSTRACT
Copper-mediated [3 + 2] annulation of alkenes with α-nitrobenzyl bromides has been developed. The reaction is promoted simply by a copper salt to produce the corresponding 2-isoxazoline N-oxides with perfect regioselectivity. The present method can be conducted under mild conditions, affording a diverse array of 2-isoxazoline N-oxides. The obtained products can readily be converted to the related heterocycles such as 2-isoxazoline and isoxazole. A radical-polar crossover pathway initiated by single-electron transfer from nitronate to a copper salt is proposed.
ABSTRACT
An abundant and low toxicity iron catalyst has enabled regioselective annulation of alkenes with α-halocarboxylic acids and their derivatives. The reaction proceeds smoothly without any additional ligands, bases, and additives to afford a variety of γ-lactones in good yields. A proposed reaction pathway through radical annulation is supported by some mechanistic studies, involving radical clock and isotope labeling experiments. The present method was applied to the practical iron-powder-promoted synthesis of γ-lactones.
