Click here for Cu/C: Copper‐in‐charcoal (Cu/C) is an active catalyst for effecting click reactions between organic azides and 1‐alkynes. Rates of cycloaddition are increased dramatically when carried out in the presence of Et3N or using microwave assistance. There is no sensitivity to air or moisture, and the catalyst can be recycled several times without loss of activity or selectivity for the 1,4‐adduct.

A nonionic amphiphile such as Triton X-100 or the vitamin E-based PTS, both of which form nanomicelles in water, promotes Heck cross-couplings of non-water-soluble partners at ambient temperatures. These are the first examples of Heck reactions conducted in water (as the only solvent) at room temperature.

The remarkable effects of added salts on the properties of aqueous micelles derived from the amphiphile PTS are described. Most notably Heck reactions run in the presence of NaCl lead to couplings on aryl bromides in water at room temperature. Olefin cross- and ring-closing metathesis reactions run in the presence of small amounts of pH-lowering KHSO4 are also accelerated, another phenomenon that does not apply to typical processes in organic media. These salt effects allow, in general, for synthetically valuable C-C bond-forming processes to be conducted under environmentally benign conditions. Recycling of the surfactant is also demonstrated.

Complexing catalytic amounts of CuH with a nonracemic JOSIPHOS or SEGPHOS ligand, together with stoichiometric PMHS, leads to exceedingly efficient and highly enantioselective 1,4-reductions of beta,beta-disubstituted enoates and lactones. An unprecedented substrate-to-ligand ratio of 7700:1 for this type of reaction is documented.

The synthesis of isomeric, functionalized 4-vinyl-1,2,3-triazole and 5-vinyl-1,2,3-triazole monomers is demonstrated using heterogeneous copper (copper-in-charcoal)-catalyzed azide−alkyne cycloaddition (CuAAC) or homogeneous ruthenium (Ru)-catalyzed azide−alkyne cycloadditions (RuAAC) “click” protocols. These reactions are regiospecific, exclusively forming 1,4- and 1,5-disubstituted triazoles as determined by 1H NMR, 13C NMR, and X-ray crystallography analysis. Polymerizations were performed using living free radical procedures to yield materials with divergent properties. In the case of the 1,5-triazole materials, glass transition temperature were significantly higher that for the 1,4-derivatives while solubility was decreased.