Theoretical Studies on the Reaction Mechanism for the Cycloaddition of Zwitterionic π-Allenyl Palladium Species: Substrate-Controlled Isomerization DOI Creative Commons

Yong-Jie Long,

Jiahao Shen, Min Shi

и другие.

Molecules, Год журнала: 2024, Номер 30(1), С. 103 - 103

Опубликована: Дек. 30, 2024

Zwitterionic π-allenyl palladium species are newly developed intermediates. A substrate-controlled step existed in the cycloaddition of zwitterionic with tropsulfimides or tropones. With assistance previously experimental studies, allenyl/propargyl was provenly found by HRMS. Further DFT calculation studies show that generated through oxidative addition Pd(0), which can be promoted Lewis acid like Yb(OTf)3, and more likely undergoes an outer sphere nucleophilic attack. The isomerization is caused difference dissociation energy between intermediation tropones, forming specificity.

Язык: Английский

A Divergent Synthesis of Spiroindenes via Ligand‐Controlled [3+2]/[4+2] Cycloadditions of Zwitterionic π‐Propargyl Palladium Species with Benzofulvenes DOI Open Access

Yong-Jie Long,

Xian-Hua Zhong,

Min Shi

и другие.

Chinese Journal of Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 5, 2025

Comprehensive Summary A divergent synthesis of spiroindenes through a palladium catalyzed cycloaddition between zwitterionic π‐propargyl species and benzofulvenes in moderate to good yields has been disclosed along with functional group compatibility broad substrate universality. This protocol features highly regioselective switchable process [3+2] [4+2] cycloadditions controlled by phosphine ligands different bite angles. The reaction mechanism clarified mechanistic studies DFT calculations, rendering that the coordination modes substrates angle play critical roles product regioselectivity.

Язык: Английский

Процитировано

2

Controlled chain-growth polymerization via propargyl/allenyl palladium intermediates DOI Creative Commons

Zheng-Lin Wang,

Rong Zhu

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Март 13, 2025

In contrast to allyl palladium complexes, propargylic/allenylic species display complex reactivities that limit their implementation in polymer chemistry, especially for chain-growth polymerizations. Here we report an example of controlled polymerization via propargyl/allenyl intermediates. Vinylidenecyclopropane 1,1-dicarboxylate (VDCP), a unique allenylic electrophile, selectively reacts the σ-allenyl rather than more common π-propargyl pathway, thereby unlocking process. Based on this concept, precise synthesis alkyne-backbone polymers is realized, featuring fast rate, high molecular weight, narrow dispersity, chemoselectivity, and excellent end-group fidelity. We demonstrate preparation unsaturated macromolecules with advanced sequences architectures using method, including block, gradient, graft copolymers. chemistry. Here, authors

Язык: Английский

Процитировано

0

“Cesium Effect”-Mediated/Controlled Divergent Synthesis via Synergistic Pd/Cu-Catalyzed Cascade Reactions DOI

Xian-Hua Zhong,

Yong-Jie Long,

Yin Wei

и другие.

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 8390 - 8402

Опубликована: Май 5, 2025

Язык: Английский

Процитировано

0

Mechanistic Investigation of the Pseudo-Halogen Effect in Enantioselective Aminocatalyzed [6 + 4] and [10 + 6] Cycloadditions: Enabling Unique Favorskii-Like Rearrangements DOI
Casper L. Barløse, René S. Bitsch, Jonas Faghtmann

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 28, 2024

A mechanistic investigation into the novel combination of

Язык: Английский

Процитировано

1

Theoretical Studies on the Reaction Mechanism for the Cycloaddition of Zwitterionic π-Allenyl Palladium Species: Substrate-Controlled Isomerization DOI Creative Commons

Yong-Jie Long,

Jiahao Shen, Min Shi

и другие.

Molecules, Год журнала: 2024, Номер 30(1), С. 103 - 103

Опубликована: Дек. 30, 2024

Zwitterionic π-allenyl palladium species are newly developed intermediates. A substrate-controlled step existed in the cycloaddition of zwitterionic with tropsulfimides or tropones. With assistance previously experimental studies, allenyl/propargyl was provenly found by HRMS. Further DFT calculation studies show that generated through oxidative addition Pd(0), which can be promoted Lewis acid like Yb(OTf)3, and more likely undergoes an outer sphere nucleophilic attack. The isomerization is caused difference dissociation energy between intermediation tropones, forming specificity.

Язык: Английский

Процитировано

1