A theoretical study on synthesis mechanisms of α,β-unsaturated carbon γ-amino ester catalyzed by PPh3

Xu, Hao; Li, Yue; Zhu, Yanyan; Shang, Xuchen; Zhu, Zhenhua; Tang, Mingsheng

doi:10.1007/s11224-017-0990-3

Cited by 4 publications

(1 citation statement)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…(3) Which step is the stereoselectivity‐determining step of chiral phosphine‐catalyzed [4 + 2] reaction? In order to solve the above mentioned problems, we intend to carry out a theoretical study on this kind of reaction by using the DFT method, which has been proved to be an effective and powerful tool for the mechanistic study of organocatalytic, [ 36–43 ] transition‐metal catalyzed [ 44–46 ] reactions.…”

Section: Introductionmentioning

confidence: 99%

Theoretical insights into phosphine‐catalyzed [4 + 2] annulation of allenoates with thiazolone‐derived alkenes

Hao

Wang

et al. 2021

J of Physical Organic Chem

Self Cite

View full text Add to dashboard Cite

In this article, the mechanism of [4 + 2] annulation of allenoates with thiazolone‐derived alkenes catalyzed by phosphine has been studied using density functional theory (DFT). This work adopted the two different phosphine catalysts (named as Cat1 and Cat2) to participate in the theoretical calculation. Catalyst Cat1 was used as a chiral catalyst to obtain optically active products in good yield with excellent enantioselectivity. With the use of Cat2 as the achiral catalyst, products were not enantioselective. The calculated results indicate that the CC bond formation is not only the rate‐determining step but also the stereoselectivity‐determining step. The R‐configured product is predicted as the dominant product catalyzed by Cat1, which is consistent with the experimental results. Moreover, global reaction index (GRI), natural bond orbital (NBO), and frontier molecular orbital (FMO) analyses indicate that the phosphine catalyst can enhance the nucleophilicity of reactant R1 and reduce the energy gap of the interacting HOMO and LUMO orbitals. The revealed mechanism would provide valuable clues in novel catalyst design.

show abstract

Section: Introductionmentioning

confidence: 99%

Theoretical insights into phosphine‐catalyzed [4 + 2] annulation of allenoates with thiazolone‐derived alkenes

Hao

Wang

et al. 2021

J of Physical Organic Chem

Self Cite

View full text Add to dashboard Cite

show abstract

Mechanisms of phosphine‐catalyzed [4 + 3] annulation of allenoates with C, N‐cyclic azomethine imines: A DFT investigation

Zhu

Guo

et al. 2018

Int J of Quantum Chemistry

Self Cite

View full text Add to dashboard Cite

In this article, mechanisms of phosphine‐catalyzed [4 + 3] annulation of allenoates with C, N‐cyclic azomethine imines have been investigated using density functional theory. The catalytic cycle for the title reaction consists of five steps. Namely, the first step is the nucleophilic addition of phosphine catalyst, the second one is the CC bond formation, the third one is the proton transfer process, and the next one is the ring‐closure process, the last one is dissociation of the catalyst and the product generation. The calculated results indicate that the nucleophilic addition of phosphine catalyst is rate‐determining. With the use of Cat as the chiral catalyst, optically active products were obtained in good yields with excellent enantioselectivities while the CC bond formation is stereoselectivity‐determining. Furthermore, the theoretically predicted the main product is SS configuration, which is in good agreement with the experimental results. The special role of the catalysts and origin of stereoselectivity was also identified by NBO, GRI, and FMO analyses. This work might be helpful for understanding the significant roles of phosphine catalyst and thus provide valuable insights on the rational design of potential catalysts for this kind of reactions.

show abstract

Interplay of thermochemistry and Structural Chemistry, the journal (volume 28, 2017, issues 5–6), and the discipline

2018

View full text Add to dashboard Cite

A theoretical study on synthesis mechanisms of α,β-unsaturated carbon γ-amino ester catalyzed by PPh3

Cited by 4 publications

References 35 publications

Theoretical insights into phosphine‐catalyzed [4 + 2] annulation of allenoates with thiazolone‐derived alkenes

Theoretical insights into phosphine‐catalyzed [4 + 2] annulation of allenoates with thiazolone‐derived alkenes

Mechanisms of phosphine‐catalyzed [4 + 3] annulation of allenoates with C, N‐cyclic azomethine imines: A DFT investigation

Interplay of thermochemistry and Structural Chemistry, the journal (volume 28, 2017, issues 5–6), and the discipline

Contact Info

Product

Resources

About