Generalization of Titanocene-Catalyzed Arylation of Epoxides through Radical Polar Crossover by Consecutive Paired Electrolysis

Niklas Schmickler

doi:10.1021/jacsau.6c00215

Generalization of Titanocene-Catalyzed Arylation of Epoxides through Radical Polar Crossover by Consecutive Paired Electrolysis

2026-06-11

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OA

AI

N

Niklas Schmickler

D

Darryl F. Nater

S

Siegfried R. Waldvogel *

A

Andreas Gansäuer *

DOI：10.1021/jacsau.6c00215

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Abstract

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Here, we describe the merging of titanocene-catalyzed radical arylation with electro-organic synthesis that combines the advantages of both fields. The critical mechanistic issue of the titanocene-catalyzed radical arylation, the efficiency of rearomatization by a proton-coupled electron transfer, can be efficiently resolved via a radical polar crossover. This is achieved in a unique manner by consecutive paired galvanostatic electrolysis through a decoupling of the electron and proton transfer steps by spatially separating the critical redox processes, the anodic oxidation of the radical σ-complex to the cationic σ-complex, and the mild in situ preparation of the active catalyst by cathodic reduction of Cp2TiCl2.

Keywords:

Arylation

Catalysts

Electrolysis

Oxidation

Redox reactions

galvanostatic electrolysis

radical σ-complex

cationic σ-complex

electro-organic synthesis

Generalization of Titanocene-Catalyzed Arylation of Epoxides through Radical Polar Crossover by Consecutive Paired Electrolysis

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