Oxidative Addition of (Hetero)aryl (Pseudo)halides at Palladium(0): Origin and Significance of Divergent Mechanisms DOI Creative Commons
Matthew J. Kania, Albert Reyes, Sharon R. Neufeldt

et al.

Published: April 1, 2024

Two limiting mechanisms are possible for oxidative addition of (hetero)aryl (pseudo)halides at Pd(0): a 3-centered concerted and nucleophilic displacement mechanism. Until now, there has been little understanding about when each mechanism is relevant. Prior investigations to distinguish between these pathways were limited few specific combinations substrate ligand. Here, we computationally evaluated over 150 transition structures in order determine mechanistic trends based on substrate, ligand(s), coordination number. Natural abundance 13C kinetic isotope effects provide experimental results consistent with computational predictions. Key findings include that (1) differences HOMO symmetries dictate that, although 12e– PdL strongly biased toward mechanism, 14e– PdL2 often prefers mechanism; (2) ligand electronics sterics, including bite angle, influence the preferred reaction PdL2; (3) phenyl triflate always reacts through regardless catalyst structure due stability anion inability oxygen effectively donate electron density Pd; (4) high reactivity C—X bonds adjacent nitrogen pyridine substrates relates stereoelectronic stabilization state. This work implications controlling rate selectivity catalytic couplings, demonstrate application insight chemodivergent cross-couplings bromochloroheteroarenes.

Language: Английский

Sequentially Regulating the Structural Transformation of Copper Metal–Organic Frameworks (Cu-MOFs) for Controlling Site-Selective Reaction DOI

Qi Qin,

Di Wang, Zhichao Shao

et al.

ACS Applied Materials & Interfaces, Journal Year: 2022, Volume and Issue: 14(32), P. 36845 - 36854

Published: Aug. 8, 2022

Regulating atomically precise sites in catalysts to achieve site-selective reactions is remarkable but challenging. In this work, a convenient and facile solid–gas/liquid reaction strategy was used construct controllable active metal–organic frameworks (MOFs) guide an orientation reaction. A flexible CuI-MOF-1 with dynamics originating from anionic tailorable framework could undergo reversible structural transformation engineer topologically equivalent mixed-valent CuICuII-MOF-2 via oxidation/reduction process. More importantly, further execute the under ammonia vapor/solution generate CuII-MOF-3. Furthermore, CuII-MOF-3 served as facilitate realize direct C–N bond arylations. The results demonstrated that possessed well-defined platforms uniformly accurately attain "turn-on/off" process different routes, providing desired ring-opening products.

Language: Английский

Citations

16
Heterocyclic Suzuki–Miyaura coupling reaction of metalla-aromatics and mechanistic analysis of site selectivity DOI Creative Commons
Zuzhang Lin, Yapeng Cai, Yaowei Zhang

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(5), P. 1227 - 1233

Published: Jan. 1, 2023

We describe unique polyhalogenated heteroarene candidates for site-selective cross-coupling, which shows high catalytic performances in the functionalization of polycyclic metalla-aromatics with excellent photophysical properties.

Language: Английский

Citations

8
Mechanisms and Site Selectivity of (Het)Ar–X Oxidative Addition to Pd(0) Are Controlled by Frontier Molecular Orbital Symmetry DOI

Jingru Lu,

Nathan D. Schley, Irina Paci

et al.

Organometallics, Journal Year: 2024, Volume and Issue: unknown

Published: July 16, 2024

Language: Английский

Citations

3
Copper-Catalyzed Amination of Aryl Chlorides under Mild Reaction Conditions DOI
Han‐Jun Ai, Seoung‐Tae Kim,

Cecilia Liu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(38), P. 25949 - 25955

Published: Sept. 16, 2024

We report a mild method for the copper-catalyzed amination of aryl chlorides. Key to success was use highly sterically encumbered

Language: Английский

Citations

3
Oxidative Addition of (Hetero)aryl (Pseudo)halides at Palladium(0): Origin and Significance of Divergent Mechanisms DOI Creative Commons
Matthew J. Kania, Albert Reyes, Sharon R. Neufeldt

et al.

Published: April 1, 2024

Two limiting mechanisms are possible for oxidative addition of (hetero)aryl (pseudo)halides at Pd(0): a 3-centered concerted and nucleophilic displacement mechanism. Until now, there has been little understanding about when each mechanism is relevant. Prior investigations to distinguish between these pathways were limited few specific combinations substrate ligand. Here, we computationally evaluated over 150 transition structures in order determine mechanistic trends based on substrate, ligand(s), coordination number. Natural abundance 13C kinetic isotope effects provide experimental results consistent with computational predictions. Key findings include that (1) differences HOMO symmetries dictate that, although 12e– PdL strongly biased toward mechanism, 14e– PdL2 often prefers mechanism; (2) ligand electronics sterics, including bite angle, influence the preferred reaction PdL2; (3) phenyl triflate always reacts through regardless catalyst structure due stability anion inability oxygen effectively donate electron density Pd; (4) high reactivity C—X bonds adjacent nitrogen pyridine substrates relates stereoelectronic stabilization state. This work implications controlling rate selectivity catalytic couplings, demonstrate application insight chemodivergent cross-couplings bromochloroheteroarenes.

Language: Английский

Citations

2