The combination of photoredox catalysis with the Wolff–Kishner (WK) reaction allows the difunctionalization of carbonyl groups by a radical-carbanion relay sequence (photo-Wolff–Kishner reaction). Photoredox initiated radical addition to N-sulfonylhydrazones yields α-functionalized carbanions following the WK-type mechanism. With sulfur-centered radicals, the carbanions are further functionalized by reaction with electrophiles including CO2 and aldehydes, whereas CF3 radical addition furnishes a wide range of gem-difluoroalkenes through β-fluoride elimination of the generated α-CF3 carbanions. More than 80 substrate examples demonstrate the broad applicability of this reaction sequence. A series of investigations including radical inhibition, deuterium labeling, fluorescence quenching, cyclic voltammetry, and control experiments support the proposed radical-carbanion relay mechanism.

A copper-catalyzed decarboxylative amination/hydroamination sequence of propargylic carbamates with various nucleophiles is described for the first time. It features an earth-abundant metal catalyst, mild reaction conditions, and high efficiency. Further treatments of the resultant key intermediates using an acid or a base in one pot enable the controllable and divergent synthesis of two types of functionalized indoles. Moreover, experiments to demonstrate the synthetic potential of this methodology are performed.

A catalytic asymmetric [3+2] cycloaddition reaction of chiral palladium-containing N(1) -1,3-dipoles with methyleneindolinones has been successfully developed. The reaction allows an efficient construction of 3,3'-pyrrolinyl spirooxindoles with high yields and excellent stereoselectivities (up to 93 % yield, 19:1 d.r. and >99 % ee). A synthetic application of this methodology is demonstrated and a stereocontrol mechanism is proposed.

A reaction sequence comprising a formal [4 + 1] cycloaddition, an E1cb elimination, and an aromatization process is described in this work. By doing so, polysubstituted pyrroles were achieved from easily available chemicals, sulfur ylides, and α,β-unsaturated imines. This protocol features mild conditions, high efficiency, and wide substrate scopes.

Here, we describe a novel [3 + 2] cycloaddition of 3-substituted indoles with vinyl aziridines and vinyl epoxides that provides a straightforward approach to pyrroloindolines and furoindolines bearing vinyl groups (up to 96% yield and 9:1 dr). In contrary to previous reports involving Lewis acid activation, this work reports successful reactions based on the activation of indole using t-BuOK and BEt (triethylborane), thereby preserving the free N-H group on indoles. In addition, a gram-scale reaction and a ring-closing metatheis reaction are performed to provide good demonstrations of the synthetic utility of this approach.

Ac opper-catalyzed decarboxylative amination/ hydroamination sequence of propargylic carbamates with various nucleophiles is described for the first time.I tf eatures an earth-abundant metal catalyst, mild reaction conditions,and high efficiency.F urther treatments of the resultant key intermediates using an acid or ab ase in one pot enable the controllable and divergent synthesis of two types of functionalized indoles.M oreover,e xperiments to demonstrate the synthetic potential of this methodology are performed.

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A catalytic asymmetric cycloaddition of 1,3‐dipoles, generated in situ by ring‐opening of aziridines, with 3‐methylene‐2‐oxindoles is developed furnishing spirooxindoles in high yields and excellent stereoselectivities.