Copper-Nitroxyl-Catalyzed α-Oxygenation of Cyclic Secondary Amines Including Application to Late-Stage Functionalization.

Cyclic secondary amines are prominent subunits in pharmaceutical compounds. Methods for direct functionalization of -unprotected/unsubstituted piperidines and related heterocycles have limited precedent despite their potential to impact medicinal chemistry and organic synthesis. Herein, we report a Cu/nitroxyl co-catalyzed method for direct conversion of cyclic secondary amines to the corresponding lactams via aerobic dehydrogenation and oxidative coupling with water.

High-Throughput Discovery and Evaluation of a General Catalytic Method for -Arylation of Weakly Nucleophilic Sulfonamides.

Through targeted high-throughput experimentation (HTE), we have identified the Pd/AdBippyPhos catalyst system as an effective and general method to construct densely functionalized ,-diaryl sulfonamide motifs relevant to medicinal chemistry. AdBippyPhos is particularly effective for the installation of heteroaromatic groups. Computational steric parametrization of the investigated ligands reveals the potential importance of remote steric demand, where a large cone angle combined with an accessible Pd center is correlated to successful catalysts for C-N coupling reactions.

Magnetic and energetic properties of transition metal doped alumina.

A doped non-diamagnetic alumina (AlO) would enable the usage of cutting edge technology, such as magnetoforming, to create advanced systems that take advantage of the high chemical and physical resilience of alumina. This study elucidates the magnetic properties of Cr, Fe, Ni, and Cu doped α- and ϑ-alumina. Density functional theory was used to predict the structural, electronic, and magnetic properties of doped alumina, as well as its stability.

Optical Signature of Formation of Protein Corona in the Firefly Luciferase-CdSe Quantum Dot Complex.

Theoretical investigation of protein corona is challenging because of the size of the protein-dot complex. In this work, we have addressed this computational bottleneck by combining pseudopotential + explicitly correlated Hartree-Fock QM calculations with molecular mechanics, molecular dynamics, and Monte Carlo techniques. The optical gap of a 5 nm CdSe quantum dot (Cd1159Se1183) was computed by sequential addition of luciferase (Lu), and a red shift of 8 nm in the λmax of protein corona (CdSe-Lu7) was observed.

Effect of heterojunction on exciton binding energy and electron-hole recombination probability in CdSe/ZnS quantum dots.

Presence of heterojunctions is important for generation of free charge carriers and the dissociation of bound electron-hole pairs in semiconductor nanoparticles. This work presents a theoretical investigation of the effect of core/shell heterojunction on electron-hole interaction in CdSe/ZnS quantum dots. The excitonic wave function in the CdSe/ZnS dots was calculated using the electron-hole explicitly correlated Hartree-Fock (eh-XCHF) method and the effect of successive addition of the ZnS shell on exciton binding energy, electron-hole recombination probability, and the electron-hole separation distance was investigated.

Smooth heuristic optimization on a complex chemical subspace.

Several algorithms for optimizing a combinatorial subspace of chemical compound space with constraints are compared. The test system is a library of organic chromophores for electro-optic applications. The constraints on the optimization include the maximization of the candidate structure hyperpolarizability while keeping the absorption within acceptable limits in the range of 400-700 nm.

Calculation of electron-hole recombination probability using explicitly correlated Hartree-Fock method.

The electron-hole explicitly correlated Hartree-Fock method (eh-XCHF) is presented as a general strategy for investigation of electron-hole correlation and computation of electron-hole recombination probability. The eh-XCHF method is a variational method which uses explicitly correlated wavefunction that depends on the electron-hole inter-particle distances. It is shown that the explicitly correlated ansatz provides a systematic route to variationally minimize the total energy.