Catalytic systems based on Ni and Pd complexes modified with chiral P-P ligands can be used in a convenient strategy for enantioselectively adding a boron unit to the beta-position of alpha,beta-unsaturated esters.

Application of a tridentate NHC containing pincer ligand to Pt catalyzed cascade cyclization reactions has allowed for the catalytic, diastereoselective cycloisomerization of biogenic alkene terminated substrates to the their polycyclic counterparts.

Reaction of a complex Pt organometallic species with electrophilic halogen sources in the presence of X– ligands changes the mechanism of reductive elimination from a concerted reductive coupling type to an SN2 type reductive elimination. In the absence of the added X– ligand the reductive elimination is stereoretentive; in its presence, the process is stereoinvertive. This selectivity hinges on the reactivity of a key five-coordinate Pt(IV) intermediate with the X– ligand.

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Results of kinetic experiments and quantum chemical computations on a series of platinum-promoted polycyclization reactions are described. Analysis of these results reveal a reactivity model that reaches beyond the energetics of the cascade itself, incorporating an ensemble of pre-cyclization conformations of the platinum-alkene reactant complex, only a subset of which are productive for bi- (or larger) cyclization and lead to products. Similarities and differences between this scenario, including reaction coordinates for polycyclization, for platinum- and enzyme-promoted polycyclization are highlighted.