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

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 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.

Language: Английский

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

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 8390 - 8402

Published: May 5, 2025

Language: Английский

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

Molecules, Journal Year: 2024, Volume and Issue: 30(1), P. 103 - 103

Published: Dec. 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.

Language: Английский