Activation Model and Origins of Selectivity for Chiral Phosphoric Acid Catalyzed Diradical Reactions

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(43), С. 23527 - 23532

Опубликована: Окт. 3, 2023

To develop new radical synthesis strategies, a profound understanding of the electronic transfer mechanism is critical. An activation model called relayed proton-coupled electron (relayed-PCET) was developed and investigated for chiral phosphoric acid-catalyzed diradical reactions by density functional theory (DFT). The driving force from nucleophile to electrophile proton that occurs via acid (CPA) catalyst electrophile. Moreover, origins selectivity can be explained distortion catalyst, favorable hydrogen bonding, strong interactions substrates with substituents CPAs.

Язык: Английский

---

Chiral phosphoric acid (CPA)-catalyzed transformation reaction of ketene: Competing mechanisms and origin of regio- and stereoselectivities

Molecular Catalysis, Год журнала: 2024, Номер 560, С. 114150 - 114150

Опубликована: Апрель 16, 2024

Язык: Английский

---

XMECP: Reaching State-of-the-Art MECP Optimization in Multiscale Complex Systems

Journal of Chemical Theory and Computation, Год журнала: 2024, Номер 20(9), С. 3590 - 3600

Опубликована: Апрель 23, 2024

The Python-based program, XMECP, is developed for realizing robust, efficient, and state-of-the-art minimum energy crossing point (MECP) optimization in multiscale complex systems. This article introduces the basic capabilities of XMECP program by theoretically investigating MECP mechanism several example systems including (1) photosensitization benzophenone, (2) photoinduced proton-coupled electron transfer cytosine-guanine base pair DNA, (3) spin-flip process oxygen activation catalyzed an iron-containing 2-oxoglutarate-dependent oxygenase (Fe/2OGX), (4) photochemical pathway flavoprotein adjusted intensity external electric field. MECPs related to multistate reaction reactivity large-scale biochemical can be well-treated workflows suggested program. branching plane updating algorithm strongly recommended as it provides derivative coupling vector (DCV) with explicit calculation equivalently evaluate contributions from non-QM residues DCV, which nonadiabatic or spin-orbit different cases. In discussed QM/MM examples, we also found that influence on QM region DCV occur through noncovalent interactions decay distance. DNA pairs, occurs across π-π stacking structure formed double-helix system. contrast general intuition, Fe/2OGX, central ferrous part contribute little coupling; however, a nearby arginine residue, treated molecular mechanics method, contributes significantly via two hydrogen bonds α-ketoglutarate (α-KG). indicates residue plays significant role activation, driving initial triplet state toward productive quintet state, more than previous knowledge bind α-KG at site bonds.

Язык: Английский

---

A general mechanistic map of organocatalytic hydroboration of alkynes: polarity controlled switchable selective pathways

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(14), С. 3952 - 3961

Опубликована: Янв. 1, 2024

A general mechanistic map for phosphine-catalyzed hydroboration of alkyne with HBpin involving multiple intermediates and competing pathways has been systematically studied by using density functional theory.

Язык: Английский

---

Theoretical Investigation on A Chiral Brønsted acid (CBA)-Catalyzed Isomerization Reaction of BCB: Mechanism and Origin of Stereoselectivity

New Journal of Chemistry, Год журнала: 2024, Номер 48(25), С. 11360 - 11365

Опубликована: Янв. 1, 2024

The mechanism, role of catalyst and origin stereoselectivity for the isomerization reaction BCB catalyzed by a chiral Brønsted acid (CBA) have been revealed in detail using DFT calculations.

Язык: Английский

---