Nuclear Quantum Effects on the Nature of Hydroboration Selectivity: Experimental Effects of First-Collision Tunneling.

The understanding of selectivity in reactions exhibiting nonstatistical dynamics is impeded by the limitations of trajectory studies with regard to nuclear quantum effects, especially tunneling. We described here the use of ring-polymer molecular dynamics (RPMD) to account for an unusual regiochemical isotope effect on the regioselectivity of hydroborations of alkenes with BH3/BD3. RPMD is able to account for the experimental observation, while statistical approaches and classical trajectories fail. The combination of experiment and RPMD trajectories suggests that tunneling in the initial collision of reactants is the major source of the nonstatistical selectivity.

Probing Catalyst Function - Electronic Modulation of Chiral Polyborate Anionic Catalysts.

Boroxinate complexes of VAPOL and VANOL are a chiral anionic platform that can serve as a versatile staging arena for asymmetric catalysis. The structural underpinning of the platform is a chiral polyborate core that covalently links together alcohols (or phenols) and vaulted biaryl ligands. The polyborate platform is assembled in situ by the substrate of the reaction, and thus a multiplex of chiral catalysts can be rapidly assembled from various alcohols (or phenols) and bis-phenol ligands for screening of catalyst activity. In the present study, variations in the steric and electronic properties of the phenol/alcohol component of the boroxinate catalyst are probed to reveal their effects on the asymmetric induction in the catalytic asymmetric aziridination reaction. A Hammett study is consistent with a mechanism in which the two substrates are hydrogen-bonded to the boroxinate core in the enantiogenic step. The results of the Hammett study are supported by a computational study in which it is found that the H-O distance of the protonated imine hydrogen bonded to the anionic boroxinate core decreases with an increase in the electron releasing ability of the phenol unit incorporated into the boroxinate. The results are not consistent with a mechanism in which the boroxinate catalyst functions as a Lewis acid and activates the imine by a Lewis acid/Lewis base interaction.