The first asymmetric insertion reactions of donor-donor carbenoids, i.e., those with no pendant electron-withdrawing groups, are reported. This process enables the synthesis of densely substituted benzodihydrofurans with high levels of enantio- and diastereoselectivity. Preliminary results show similar efficiency in the preparation of indanes. This new method is used in the first enantioselecti...

A series of modified Hoveyda-Grubbs catalysts incorporating a chelating iodo-benzylidene ligand were prepared and characterized. The presence of electron-withdrawing ring substituents in the para position to the iodide was found to decrease the catalytic activity, revealing that dissociation of the Ru···I-Ar bond is not the rate-determining step.

2-Electron-withdrawing-group-substituted 2-bromoanilides can be converted to the corresponding 3,3-disubstituted oxindoles with high efficiency under visible light irradiation by using fac-Ir(ppy)(3) as the photoredox catalyst. This protocol is suitable for the synthesis of oxindoles with chloro and bromo atoms attached to the phenyl ring.

The syntheses of the naturally occurring indolizidine alkaloid (±)-tashiromine and its unnatural epimer (±)-epitashiromine are demonstrated through the use of enaminone chemistry. The impact of various electron-withdrawing substituents at the C-8 position of the indolizidine core on the preparation of the bicyclic system is described.

Ambient light stable 3-trifluoromethyl-3-aryldiazirine photolabels are developed via stabilization of the strained three membered diazirine ring by replacing the phenyl ring with electron withdrawing heterocyclic rings. Photolabeling studies reveal that these ambient light stable photolabels are equally efficient in photolabeling target proteins as the traditional 3-trifluoromethyl-3-phenyldiaz...

Transfer hydrogenation of polarized olefins bearing strongly electron-withdrawing groups on one side of the double bond was achieved with ammonia borane under mild conditions without using a catalyst. Mechanistic studies proved the character of the direct H transfers proceeding stepwise with a unique hydroboration intermediate and hydride before proton transfer.

A straightforward and atom-economical base-free palladium-catalyzed regioselective direct arylation of coumarins and chromenones is devised. This protocol is compatible with a wide variety of electron-donating and -withdrawing substituents and allows construction of various biologically important flavone and neoflavone backbones.

Benzodithioloimines are reacted with arynes or alkynes substituted with electron-withdrawing groups to afford the corresponding thianthrene or benzo[b][1,4]dithiine derivatives. The transformation takes place under mild reaction conditions without any transition metal. Furthermore, the reaction mode could be expanded to 2-thiocyanatopyrroles yielding pyrrolothiazoles.