Enantioselective Transfer Hydrogenation of α-Methoxyimino-β-keto Esters.

α-Methoxyimino-β-keto esters are reported to undergo highly enantioselective catalytic transfer hydrogenation using the Noyori-Ikariya complex RuCl(-cymene)[(,)-Ts-DPEN] in a mixture of formic acid-triethylamine and dimethylformamide at 25 °C. The experimental study performed on over 25 substrates combined with computational analysis revealed that a -configured methoxyimino group positioned alpha to a ketone carbonyl leads to higher reactivity and mostly excellent enantioselectivity within this substrate class. Density functional theory calculations of competing transition states were used in rationalizing the origins of enantioselectivity and the possible role of the methoxyimino group in the reaction outcome.

Quantum chemical package Jaguar: A survey of recent developments and unique features.

This paper is dedicated to the quantum chemical package Jaguar, which is commercial software developed and distributed by Schrödinger, Inc. We discuss Jaguar's scientific features that are relevant to chemical research as well as describe those aspects of the program that are pertinent to the user interface, the organization of the computer code, and its maintenance and testing. Among the scientific topics that feature prominently in this paper are the quantum chemical methods grounded in the pseudospectral approach.

Quantum Simulation of Molecular Response Properties in the NISQ Era.

Accurate modeling of the response of molecular systems to an external electromagnetic field is challenging on classical computers, especially in the regime of strong electronic correlation. In this article, we develop a quantum linear response (qLR) theory to calculate molecular response properties on near-term quantum computers. Inspired by the recently developed variants of the quantum counterpart of equation of motion (qEOM) theory, the qLR formalism employs "killer condition" satisfying excitation operator manifolds that offer a number of theoretical advantages along with reduced quantum resource requirements.

Partitioning Quantum Chemistry Simulations with Clifford Circuits.

Current quantum computing hardware is restricted by the availability of only few, noisy qubits which limits the investigation of larger, more complex molecules in quantum chemistry calculations on quantum computers in the near term. In this work, we investigate the limits of their classical and near-classical treatment while staying within the framework of quantum circuits and the variational quantum eigensolver. To this end, we consider naive and physically motivated, classically efficient product ansatz for the parametrized wavefunction adapting the separable-pair ansatz form.

Pressurized Formic Acid Dehydrogenation: An Entropic Spring Replaces Hydrogen Compression Cost.

Formic acid is unique among liquid organic hydrogen carriers (LOHCs), because its dehydrogenation is highly entropically driven. This enables the evolution of high-pressure hydrogen at mild temperatures that is difficult to achieve with other LOHCs, conceptually by releasing the "spring" of energy stored entropically in the liquid carrier. Applications calling for hydrogen-on-demand, such as vehicle filling, require pressurized H.

On the existence of CO microsolvated clusters: a theoretical study.

Microsolvated clusters of multiply charged anions play a crucial role in atmospheric chemistry and some of them were previously registered experimentally. At the same time, there are no experimental observations of [CO·(HO)]. The reasons for this may be related to the thermodynamical or kinetical instability of microsolvated CO toward autoionization or autoprotonation processes.

Quantum self-consistent equation-of-motion method for computing molecular excitation energies, ionization potentials, and electron affinities on a quantum computer.

Near-term quantum computers are expected to facilitate material and chemical research through accurate molecular simulations. Several developments have already shown that accurate ground-state energies for small molecules can be evaluated on present-day quantum devices. Although electronically excited states play a vital role in chemical processes and applications, the search for a reliable and practical approach for routine excited-state calculations on near-term quantum devices is ongoing.

Catalytic Stereoconvergent Synthesis of Homochiral β-CF, β-SCF, and β-OCF Benzylic Alcohols.

We describe an efficient catalytic strategy for enantio- and diastereoselective synthesis of homochiral β-CF, β-SCF, and β-OCF benzylic alcohols. The approach is based on dynamic kinetic resolution (DKR) with Noyori-Ikariya asymmetric transfer hydrogenation leading to simultaneous construction of two contiguous stereogenic centers with up to 99.9% ee, up to 99.

Molecular dynamics on quantum annealers.

In this work we demonstrate a practical prospect of using quantum annealers for simulation of molecular dynamics. A methodology developed for this goal, dubbed Quantum Differential Equations (QDE), is applied to propagate classical trajectories for the vibration of the hydrogen molecule in several regimes: nearly harmonic, highly anharmonic, and dissociative motion. The results obtained using the D-Wave 2000Q quantum annealer are all consistent and quickly converge to the analytical reference solution.

Markovnikov alcohols via epoxide hydroboration by molecular alkali metal catalysts.

Synthesis of branched "Markovnikov" alcohols is crucial to various chemical industries. The catalytic reduction of substituted epoxides under mild conditions is a highly attractive method for preparing such alcohols. Classical methods based on heterogeneous or homogeneous transition metal-catalyzed hydrogenation, hydroboration, or hydrosilylation usually suffer from poor selectivity, reverse regioselectivity, limited functional group compatibility, high cost, and/or low availability of the catalysts.

Quantum Simulation of Molecular Electronic States with a Transcorrelated Hamiltonian: Higher Accuracy with Fewer Qubits.

Simulation of electronic structure is one of the most promising applications on noisy intermediate-scale quantum (NISQ) era devices. However, NISQ devices suffer from a number of challenges like limited qubit connectivity, short coherence times, and sizable gate error rates. Thus, desired quantum algorithms should require shallow circuit depths and low qubit counts to take advantage of these devices.

Toward a QUBO-Based Density Matrix Electronic Structure Method.

Density matrix electronic structure theory is used in many quantum chemistry methods to "alleviate" the computational cost that arises from directly using wave functions. Although density matrix based methods are computationally more efficient than wave function based methods, significant computational effort is involved. Because the Schrödinger equation needs to be solved as an eigenvalue problem, the time-to-solution scales cubically with the system size in mean-field type approaches such as Hartree-Fock and density functional theory and is solved as many times in order to reach charge or field self-consistency.

Performance Analysis of CP2K Code for Ab Initio Molecular Dynamics on CPUs and GPUs.

Using a realistic molecular catalyst system, we conduct scaling studies of ab initio molecular dynamics simulations using the popular CP2K code on both Intel Xeon CPU and NVIDIA V100 GPU architectures. Additional performance improvements were gained by finding more optimal process placement and affinity settings. Statistical methods were employed to understand performance changes in spite of the variability in runtime for each molecular dynamics timestep.

Sampling electronic structure quadratic unconstrained binary optimization problems (QUBOs) with Ocean and Mukai solvers.

The most advanced D-Wave Advantage quantum annealer has 5000+ qubits, however, every qubit is connected to a small number of neighbors. As such, implementation of a fully-connected graph results in an order of magnitude reduction in qubit count. To compensate for the reduced number of qubits, one has to rely on special heuristic software such as qbsolv, the purpose of which is to decompose a large quadratic unconstrained binary optimization (QUBO) problem into smaller pieces that fit onto a quantum annealer.

Computing molecular excited states on a D-Wave quantum annealer.

The possibility of using quantum computers for electronic structure calculations has opened up a promising avenue for computational chemistry. Towards this direction, numerous algorithmic advances have been made in the last five years. The potential of quantum annealers, which are the prototypes of adiabatic quantum computers, is yet to be fully explored.

Mechanism of Potassium -Butoxide-Catalyzed Ketones Hydrogenation in the Solution Phase.

The mechanism of ketones homogeneous hydrogenation with -BuOK in -butanol is currently portrayed as the one proceeding via a six-membered [2 + 2 + 2] cyclic transition state involving the H molecule, the base, and a ketone. However, the concerted nature of the reaction is inconsistent with a number of experimental observations. Here we reanalyze available experimental data and revise the mechanism of this paradigmatic reaction based on the static and dynamic density functional theory (DFT) calculations in solution phase.

Reduction of the molecular hamiltonian matrix using quantum community detection.

Quantum chemistry is interested in calculating ground and excited states of molecular systems by solving the electronic Schrödinger equation. The exact numerical solution of this equation, frequently represented as an eigenvalue problem, remains unfeasible for most molecules and requires approximate methods. In this paper we introduce the use of Quantum Community Detection performed using the D-Wave quantum annealer to reduce the molecular Hamiltonian matrix in Slater determinant basis without chemical knowledge.

Electronic structure with direct diagonalization on a D-wave quantum annealer.

Quantum chemistry is regarded to be one of the first disciplines that will be revolutionized by quantum computing. Although universal quantum computers of practical scale may be years away, various approaches are currently being pursued to solve quantum chemistry problems on near-term gate-based quantum computers and quantum annealers by developing the appropriate algorithm and software base. This work implements the general Quantum Annealer Eigensolver (QAE) algorithm to solve the molecular electronic Hamiltonian eigenvalue-eigenvector problem on a D-Wave 2000Q quantum annealer.

Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of C═X (X = O, N) Functionalities.

Catalysis is the second largest application for V after its use as an additive to improve steel production. Molecular complexes of vanadium(V) are particularly useful and efficient catalysts for oxidation processes; however, their ability to catalyze reductive transformations has yet to be fully explored. Here we report the first examples of polar organic functionality reduction mediated by V.

Cleavage of N-H Bond of Ammonia via Metal-Ligand Cooperation Enables Rational Design of a Conceptually New Noyori-Ikariya Catalyst.

The asymmetric transfer hydrogenation (ATH) of ketones/imines with Noyori-Ikariya catalyst represents an important reaction in both academia and fine chemical industry. The method allows for the preparation of chiral secondary alcohols/amines with very good to excellent optical purities. Remarkably, the same chiral Noyori-Ikariya complex is also a precatalyst for a wide range of other chemo- and stereoselective reductive and oxidative transformations.

Why Does Alkylation of the N-H Functionality within M/NH Bifunctional Noyori-Type Catalysts Lead to Turnover?

Molecular metal/NH bifunctional Noyori-type catalysts are remarkable in that they are among the most efficient artificial catalysts developed to date for the hydrogenation of carbonyl functionalities (loadings up to ∼10 mol %). In addition, these catalysts typically exhibit high C═O/C═C chemo- and enantioselectivities. This unique set of properties is traditionally associated with the operation of an unconventional mechanism for homogeneous catalysts in which the chelating ligand plays a key role in facilitating the catalytic reaction and enabling the aforementioned selectivities by delivering/accepting a proton (H) via its N-H bond cleavage/formation.

The mechanism of enantioselective ketone reduction with Noyori and Noyori-Ikariya bifunctional catalysts.

The catalytic hydrogenation of prochiral ketones with second and third-row transition metal complexes bearing chelating chiral ligands containing at least one N-H functionality has achieved unparalleled performance, delivering, in the best cases, chiral alcohols with up to 99.9% ee using extremely small catalyst loadings (∼10(-5) mol%). Hence the efficacy of this reaction has closely approached that of natural enzymatic systems and the reaction itself has become one of the most efficient artificial catalytic reactions developed to date.

First-row transition metal complexes of ENENES ligands: the ability of the thioether donor to impact the coordination chemistry.

The reactions of two variants of ENENES ligands, E(CH2)2NH(CH)2SR, where E = 4-morpholinyl, R = Ph (), Bn () with MCl2 (M = Mn, Fe, Co, Ni and Cu) in coordinating solvents (MeCN, EtOH) affords isolable complexes, whose magnetic susceptibility measurements suggest paramagnetism and a high-spin formulation. X-Ray diffraction studies of available crystals show that the ligand coordinates to the metal in either a bidentate κ(2)[N,N'] or tridentate κ(3)[N,N',S] fashion, depending on the nature of ligand and/or identity of the metal atom. In the case of a less basic SPh moiety, a bidentate coordination mode was identified for harder metals (Mn, Fe), whereas a tridentate coordination mode was identified in the case of a more basic SBn moiety with softer metals (Ni, Cu).