‘Ring-Walking’ Aryl Cross-Coupling Reactions Involving Palladium Aryne Intermediates DOI
Richard Y. Liu, E. Bayer,

Yoshiya Sekiguchi

и другие.

Synlett, Год журнала: 2025, Номер unknown

Опубликована: Апрель 11, 2025

Abstract The regiospecificity of conventional cross-coupling reactions, though advantageous for its predictability and retrosynthetic simplicity, constrains chemical-space exploration. Discovery efforts have become biased toward examining substitution patterns which coupling partners are readily obtainable. To address this problem, we developed a migratory (‘ring-walking’) approach that integrates the isomerization arylpalladium(II) intermediates into catalytic cycles. A reversible was achieved through ligand design use cesium fluoride as base, process then combined with dynamic kinetic resolution regioisomeric aryl halides broad range oxygen- nitrogen-centered nucleophiles. method permits rapid access to meta-substituted arenes from para-substituted electrophiles. This account summarizes key mechanistic principles established during development these reactions.

Язык: Английский

Synthesis of benzoheterocycles by palladium-catalyzed migratory cyclization through an unexpected reaction cascade DOI Creative Commons
Wencong Li, Lin Zhang,

Shiming Bai

и другие.

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

Опубликована: Апрель 9, 2025

Migratory functionalization of C-H bonds through metal migration from carbon to under transition catalysis is a process significant academic and industrial interest. Herein, palladium-catalyzed migratory cyclization α-bromoalkene derivatives ArXCBr=CH2, in which X denotes phosphorus (P(O)R), silicon (SiR2), sulfur (SO2), (C(O)), nitrogen (NTs), or oxygen-based moiety, affording various benzoheterocyclic compounds has been developed. Mechanistic investigations have demonstrated that the reaction proceeds an unexpected cascade, with trans-1,2-palladium between sp2 carbons being key step catalytic cycle. To best our knowledge, this type not reported previously.

Язык: Английский

Процитировано

0
‘Ring-Walking’ Aryl Cross-Coupling Reactions Involving Palladium Aryne Intermediates DOI
Richard Y. Liu, E. Bayer,

Yoshiya Sekiguchi

и другие.

Synlett, Год журнала: 2025, Номер unknown

Опубликована: Апрель 11, 2025

Abstract The regiospecificity of conventional cross-coupling reactions, though advantageous for its predictability and retrosynthetic simplicity, constrains chemical-space exploration. Discovery efforts have become biased toward examining substitution patterns which coupling partners are readily obtainable. To address this problem, we developed a migratory (‘ring-walking’) approach that integrates the isomerization arylpalladium(II) intermediates into catalytic cycles. A reversible was achieved through ligand design use cesium fluoride as base, process then combined with dynamic kinetic resolution regioisomeric aryl halides broad range oxygen- nitrogen-centered nucleophiles. method permits rapid access to meta-substituted arenes from para-substituted electrophiles. This account summarizes key mechanistic principles established during development these reactions.

Язык: Английский

Процитировано

0