2023
DOI: 10.1021/jacs.3c00685
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Kinetic, Thermodynamic, and Dynamic Control in Normal vs. Cross [2 + 2] Cycloadditions of Ene-Keteniminium Ions: Computational Understanding, Prediction, and Experimental Verification

Abstract: Almost all reported intramolecular [2 + 2] reactions of ene-keteniminium ions gave normal [2 + 2] products with a fused bicycle framework, but not cross [2 + 2] products with a bicyclo[3.1.1]heptane skeleton, a highly pursued bioisostere in pharmaceutical chemistry. How to rationalize this and design new cross [2 + 2] reactions? Theoretical studies using density functional theory, high-level ab initio single-point energy calculations, and molecular dynamics showed that this [2 + 2] reaction has all three patte… Show more

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Cited by 8 publications
(4 citation statements)
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“…The ωB97X-D functional was chosen for its high accuracy in simulating keteniminium ion-related reactions (see the SI for more discussion). 3 Unscaled harmonic frequency calculations at the same level were performed to validate each structure as either a minimum or a transition state and to evaluate its zeropoint energy and thermal corrections at 298.15 K. Intrinsic reaction coordinate (IRC) 9 calculations were carried out to confirm the transition states connecting the right reactant(s) and product(s). High-level single-point energies were calculated at the DLPNO−CCSD(T) 10 /def2-TZVPP 8 (with the def2-TZVPP/C 11 auxiliary basis set; "TightPNO" and "TightSCF" settings were used) level using the ORCA 4.2.1 12 software package.…”
Section: ■ Computational Methodsmentioning
confidence: 99%
See 2 more Smart Citations
“…The ωB97X-D functional was chosen for its high accuracy in simulating keteniminium ion-related reactions (see the SI for more discussion). 3 Unscaled harmonic frequency calculations at the same level were performed to validate each structure as either a minimum or a transition state and to evaluate its zeropoint energy and thermal corrections at 298.15 K. Intrinsic reaction coordinate (IRC) 9 calculations were carried out to confirm the transition states connecting the right reactant(s) and product(s). High-level single-point energies were calculated at the DLPNO−CCSD(T) 10 /def2-TZVPP 8 (with the def2-TZVPP/C 11 auxiliary basis set; "TightPNO" and "TightSCF" settings were used) level using the ORCA 4.2.1 12 software package.…”
Section: ■ Computational Methodsmentioning
confidence: 99%
“…Structure optimizations were performed at the SMD­(DCM)/ωB97X-D/def2-SVP level of theory, unless otherwise specified. The ωB97X-D functional was chosen for its high accuracy in simulating keteniminium ion-related reactions (see the SI for more discussion) . Unscaled harmonic frequency calculations at the same level were performed to validate each structure as either a minimum or a transition state and to evaluate its zero-point energy and thermal corrections at 298.15 K. Intrinsic reaction coordinate (IRC) calculations were carried out to confirm the transition states connecting the right reactant(s) and product(s).…”
Section: Methodsmentioning
confidence: 99%
See 1 more Smart Citation
“…A mechanistic insight into chemical reactions tracks the transformation of reactants into products and plays a crucial role in the physical perception of the reaction and predicting the most plausible product. The sophisticated analytical techniques currently available are either expensive, time-consuming or unable to detect very fast, highly exoergic reactions, and highly unstable transition states (TSs). Theoretical simulation aided by experimental evidence is the inexpensive and best-determining tool for the fundamental understanding of the reaction mechanisms. ,,,,, …”
Section: Introductionmentioning
confidence: 99%