Nucleophilic attack on carbon-based electrophiles is a central reactivity paradigm in chemistry and biology. The steric and electronic properties of the electrophile dictate its reactivity with different nucleophiles of interest, allowing the opportunity to fine-tune electrophiles for use as coupling partners in multistep organic synthesis or for covalent modification of proteins in drug discovery. Reactions that directly transform inexpensive chemical feedstocks into versatile carbon electrophiles would therefore be highly enabling. Herein, we report the catalytic, regioselective oxidative cyanation of conjugated and nonconjugated alkenes using a homogeneous copper catalyst and a bystanding N-F oxidant to furnish branched alkenyl nitriles that are difficult to prepare using existing methods. We show that the alkenyl nitrile products serve as electrophilic reaction partners for both organic synthesis and the chemical proteomic discovery of covalent protein ligands.

A method to achieve enantioselective 1,4-hydroboration of terminal enynes to access allenyl boronates under CuH catalysis is described. The reaction typically proceeds in a highly stereoselective manner and tolerates an array of synthetically useful functional groups. The utility of the enantioenriched allenyl boronate products is demonstrated through several representative downstream derivatizations.

A method to achieve enantioselective 1,4-hydroboration of terminal enynes to access allenyl boronates under CuH catalysis is described. The reaction typically proceeds in a highly stereoselective manner and tolerates an array of synthetically useful functional groups. The utility of the enantioenriched allenyl boronate products is demonstrated through several representative downstream derivatizations.

Palladium-catalyzed cross-coupling reactions of N-tosylhydrazones and arylbromides have been applied for the first time in the synthesis of cross-conjugated polymers, namely poly(arylene-1,1-vinylidene)s (iso-PAVs).

Three-component polymerization based on the Hooz reaction has been developed for the first time. Under mild conditions (0−40 °C, catalyst-free), the reaction of dialdehydes, bisdiazocarbonyl compounds, and trialkylboron leads to the formation of poly(βhydroxyketone)s. The number-average molecular weight (M n ) is up to 31.2 kg mol −1 , and the yield is up to 97%. The β-hydroxyketone structure in poly(β-hydroxyketone)s enables highly efficient polymer degradation under alkaline conditions, with the isolation of dialdehydes for recycling. The hydroxyl groups in the polymer also provide the possibility for postpolymerization modifications, including cross-linking, acetylation, and oxidation.

The copper-catalyzed cross-coupling of alkynes and α-diazoesters have been applied in the synthesis of polyallenoates for the first time. The polymerization tolerated various functional groups and afforded the polyallenoates with...

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Cu(I)-catalyzed Doyle-Kirmse reaction has been successfully introduced into polymer chemistry for the first time. A series of new type of sulfur-containing polymers were efficiently synthesized from various allyl sulfides and...