DFT Studies on the Mechanisms of Carboamination/Diamination of Unactivated Alkenes Mediated by Pd(IV) Intermediates.

Density functional theory (DFT) calculations have been employed to investigate the mechanism of carboamination and diamination of unactivated alkenes mediated by Pd(IV) intermediates. Both reactions share a common Pd(IV) intermediate, serving as the starting point for either the carboamination or the diamination pathway. The formation of this Pd(IV) intermediate encompasses a transition state that substantially impacts the turnover frequency (TOF) of catalytic cycles, with an apparent activation free-energy barrier of 26.1 kcal mol-1. Carboamination of unactivated alkenes proceeds through the coordination of a toluene molecule, C-H activation, inner reductive elimination, and the separation of the carboamination product from this intermediate, while diamination of unactivated alkenes involves the formation of the ion nucleophile, SN2 attack, and the separation of the diamination product. A comparison of the free-energy profiles for carboamination and diamination of unactivated alkenes can elucidate the origin of the chemoselectivity, and Bader's atoms in molecules (AIM) wave function analyses have been performed to analyze the contributions of the outer C-N bonding in the diamination process.

The treatment of dispersion terms for solution systems.

DFT calculations of reaction mechanisms in solution have always been a hot topic, especially for transition-metal-catalyzed reactions, in which the traditional DFT-D3 method has been extensively employed. The overestimation of the dispersion from the traditional DFT-D3 method leads to a quite low activation free-energy barrier, so it is worth finding a proper way to deal with the dispersion for solution systems. The solvent-solute dispersion is also important for solution systems, and thus it should be calculated together with the solute dispersion. The newly generated solute-solute dispersion energy should be shared equally with the newly formed cavity between two interacting species; therefore, only half of the solute-solute and solvent-solute dispersion terms belong to the solute molecule. The detailed treatment of dispersion correction for solution systems has been fully addressed, and this method has been confirmed with the examples of ligand exchange reactions and catalytic reactions.

α-Stereoselective 3-Deoxy-d-manno-oct-2-ulosonoic Acid (Kdo) O-Glycosylation with a p-Toluenethioglycoside Donor by the (p-Tol)2SO/Tf2O Preactivation Strategy.

A convenient and efficient approach was developed to synthesize α-Kdo O-glycosides based on the Tf2O/(p-Tol)2SO preactivation strategy using peracetylated Kdo thioglycoside as a donor. Under the optimized reaction conditions, several O-glycoside products, including α-(2 → 1)-, α-(2 → 2)-, α-(2 → 3)-, and α-(2 → 6)-Kdo products, were stereoselectively synthesized in high yields. Remarkably, a series of aromatic α-Kdo O-glycosides were first and successfully constructed in high yields. An SN2-like mechanism was revealed by DFT calculations and experimental results.

DFT calculations in solution systems: solvation energy, dispersion energy and entropy.

DFT calculations of reaction mechanisms in solution have always been a hot topic, especially for transition-metal-catalyzed reactions. The calculation of solvation energy is performed using either the polarizable continuum model (PCM) or the universal solvation model SMD. The PCM calculation is very sensitive to the choice of atomic radii to form a cavity, where the self-consistent isodensity PCM (SCI-PCM) has been recognized as the best choice and our IDSCRF radii can provide a similar cavity. Moving from a gas-phase case to a solution case, dispersion energy and entropy should be carefully treated. The solvent-solute dispersion is also important in solution systems, and it should be calculated together with the solute dispersion. Only half of the solvent-solute dispersion energy from the PCM calculation belongs to the solute molecules to maintain a thermal equilibrium between a solute molecule and its cavity, similar to the treatment of electrostatic energy. Relative solute dispersion energy should also be shared equally with the newly formed cavity. The entropy change from a gas phase to a liquid phase is quite large, but the modern quantum chemistry programs can only calculate the gas-phase translational entropy based on the idea-gas equation. In this review, we will provide an operable method to calculate the solution translational entropy, which has been coded in our THERMO program.

Controllable syntheses of B/N anionic aminoborane chain complexes by the reaction of NH3BH3 with NaH and the mechanistic study.

B/N anionic aminoborane linear or branched chain complexes, [BH3(NH2BH2)nH]- (n = 1, 2, and 3) and [BH(NH2BH3)3]-, have been synthesized through the controlled reactions of ammonia borane (NH3BH3) with NaH by adjusting the reactant ratios and reaction temperatures. The possible reaction mechanisms were elucidated based on experimental and theoretical studies.

Insight into Isothiourea-Catalyzed Enantioselective Addition of Saturated Esters to Iminium Ions.

The possible mechanisms and origin of the selectivities of isothiourea-catalyzed addition of saturated esters to iminium ions have been investigated by density functional theory. The favorable reaction pathway includes three stages: formation of an ammonium enolate intermediate, enantioselective addition of the ammonium enolate intermediate to the iminium ion, and dissociation of the catalyst to form the product. The enantioselective addition process is the stereoselectivity-determining step, while the chemoselectivity-determining step is included in the formation of the final product. The calculated energy barriers show that the chemoselectivity is thermodynamically controlled, and it depends on the polarities of the products and the nucleophilicities of the N atoms of the enamine reactant moieties of the intermediates. The origin of the stereoselectivity was investigated by non-covalent interaction analysis of the key transition states. Hydrogen bonding interactions were identified as the determining factor for controlling the stereoselectivity. The obtained insight will be valuable for rational design of novel Lewis base organocatalyst-promoted enantioselective addition reactions with special chemoselectivities.

Correction: Unravelling a general mechanism of converting ionic B/N complexes into neutral B/N analogues of alkanes: Hδ+Hδ- dihydrogen bonding assisted dehydrogenation.

Correction for 'Unravelling a general mechanism of converting ionic B/N complexes into neutral B/N analogues of alkanes: Hδ+Hδ- dihydrogen bonding assisted dehydrogenation' by Xi-Meng Chen et al., Chem. Commun., 2019, 55, 12239-12242.

Unravelling a general mechanism of converting ionic B/N complexes into neutral B/N analogues of alkanes: Hδ+Hδ- dihydrogen bonding assisted dehydrogenation.

Long-sought mechanisms for the conversion of diammoniate of diborane ([NH3BH2NH3]+[BH4]-) into NH3BH3 and [NH2BH2]n as well as ammonium aminodiborane ([NH4]+[BH3NH2BH3]-) into a butane analogue, NH3BH2NH2BH3, have been elucidated on the basis of extensive experimental and theoretical studies. The [NH4]+ ammonium cation and the (η2-H2)BH2R moiety are found to be critical in B/N chain expansion.