An Integrated Study of Pd(0)-Halide Interactions in Pd Oxidative Addition to Organic Halides: Uncovering the “Super Iodine” Character of Pd(0) DOI Creative Commons
Liuqun Gu

Published: Aug. 6, 2024

Pd(0) oxidative addition (OA) to organic halides is a fundamental step in many catalytic transformations. Previous mechanistic studies have shown that the electronic/steric nature of ligand, metal coordination unsaturation, halide identity and presence an additive all sizable influences on reaction reactivity selectivity. A single parameter-based rational design fully integrating important factors quantitative manner remains elusive, due complex OA. To address this challenge, study Pd(0)-halide interactions which are crucial for 3-centered concerted mechanism, initiated work by key progress organometallic chemistry relatively well-established halogen bonding knowledge, mimicking “data-driven” method. The achieved advanced understanding mechanisms includes five parts: 1) uncovering “super iodine” character Pd(0), 2) Pd-halide (organic halide) interaction its essential role Pd(organic precomplex before OA; 3) molecular mechanism effect, theoretical prediction transfer pathway OA specific halides; 4) demystifying known super ligand-controlled Pd catalysis with inactive aryl chlorides; ultimately 5) proposing proof-of-concept surface molecule electrostatic potential-based

Language: Английский

Photoredox-Catalyzed Decarboxylative Elimination via Halogen Atom Transfer DOI
Deshkanwar Brar,

Roberto Aponte,

Jon A. Tunge

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 7, 2025

Enamides and enecarbamates offer an excellent balance between stability reactivity. Decarboxylation of widely available amino acids offers a green efficient alternative to accessing these reagents. The present study describes photocatalytic approach for the direct decarboxylative synthesis enamides via sequential radical decarboxylation putative halogen-atom transfer (XAT). This operationally simple, economical protocol is scalable allows mild reaction conditions short times. In addition, it obviates need transition metals preactivation carboxylic acids.

Language: Английский

Citations

0
Cobalt‐Catalyzed Allylic Alkylation at sp3‐Carbon Centers DOI
Ebbin Joseph, Jon A. Tunge

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(47)

Published: June 13, 2024

Abstract The rising demand and financial costs of noble transition metal catalysts have emphasized the need for sustainable catalytic approaches. Over past few years, base‐metal emerged as ideal candidates to replace their noble‐metal counterparts because abundance easiness handling. Despite significant advancements achieved with precious metals, earth‐abundant cobalt efficient alternatives allylic substitution reactions. In this review, alkylations at sp 3 ‐carbon centers mediated by will be discussed, a special focus on mechanistic features, scope, limitations.

Language: Английский

Citations

1
An Integrated Study of Pd(0)-Halide Interactions in Pd Oxidative Addition to Organic Halides: Uncovering the “Super Iodine” Character of Pd(0) DOI Creative Commons
Liuqun Gu

Published: Aug. 6, 2024

Pd(0) oxidative addition (OA) to organic halides is a fundamental step in many catalytic transformations. Previous mechanistic studies have shown that the electronic/steric nature of ligand, metal coordination unsaturation, halide identity and presence an additive all sizable influences on reaction reactivity selectivity. A single parameter-based rational design fully integrating important factors quantitative manner remains elusive, due complex OA. To address this challenge, study Pd(0)-halide interactions which are crucial for 3-centered concerted mechanism, initiated work by key progress organometallic chemistry relatively well-established halogen bonding knowledge, mimicking “data-driven” method. The achieved advanced understanding mechanisms includes five parts: 1) uncovering “super iodine” character Pd(0), 2) Pd-halide (organic halide) interaction its essential role Pd(organic precomplex before OA; 3) molecular mechanism effect, theoretical prediction transfer pathway OA specific halides; 4) demystifying known super ligand-controlled Pd catalysis with inactive aryl chlorides; ultimately 5) proposing proof-of-concept surface molecule electrostatic potential-based

Language: Английский

Citations

1