Dynamic Kinetic Resolution Processes Based on the Switchable Configurational Instability of Allenyl Copper Reagents.

The configurational instability of allenyl copper reagents is unveiled. An experimental study highlights the crucial role of Li and of the reaction temperature in the control of the configurational stability of allenyl copper reagents. A judicious choice of the reaction conditions allows efficient dynamic kinetic resolution processes and gives a one-pot access to homopropargylic alcohols or amines bearing up to four contiguous defined stereogenic centers.

Mechanism of Enolate Transfer between Si and Cu.

Exchange of X (F, Cl, OMe) and a substituted enolate chain between SiMe and various Cu complexes was examined. Reaction mechanisms pass through a cyclic transition state in which the reaction coordinate is associated with rotation of the SiMe moiety. The dependence of the thermodynamic and kinetic features on the nature of the active and ancillary ligands was examined.

Preparation of monopodal and bipodal aluminum surface species by selective protonolysis of highly reactive [AlH(NMeEt)] on silica.

The synthesis and characterization of silica-grafted monopodal and bipodal aluminum hydrides has been achieved starting from 200 °C- and 700 °C-annealed silica and [AlH(NMeEt)]. The mechanism by which aluminum trishydride reacts with isolated and vicinal silanols, assisted by the amine, has been investigated computationally at the ωB97XD-DFT level.

Vertical and adiabatic excitations in anthracene from quantum Monte Carlo: Constrained energy minimization for structural and electronic excited-state properties in the JAGP ansatz.

We study the ionization energy, electron affinity, and the π → π(∗) ((1)La) excitation energy of the anthracene molecule, by means of variational quantum Monte Carlo (QMC) methods based on a Jastrow correlated antisymmetrized geminal power (JAGP) wave function, developed on molecular orbitals (MOs). The MO-based JAGP ansatz allows one to rigorously treat electron transitions, such as the HOMO → LUMO one, which underlies the (1)La excited state. We present a QMC optimization scheme able to preserve the rank of the antisymmetrized geminal power matrix, thanks to a constrained minimization with projectors built upon symmetry selected MOs.