Cross-electrophile Coupling: Principles of Reactivity and Selectivity

Overview

Journal J Org Chem

Publisher American Chemical Society

Specialty Chemistry

Date 2014 May 14

PMID 24820397

Citations 123

Authors

Daniel A Everson

Daniel J Weix

Affiliations

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Abstract

A critical overview of the catalytic joining of two different electrophiles, cross-electrophile coupling (XEC), is presented with an emphasis on the central challenge of cross-selectivity. Recent synthetic advances and mechanistic studies have shed light on four possible methods for overcoming this challenge: (1) employing an excess of one reagent; (2) electronic differentiation of starting materials; (3) catalyst-substrate steric matching; and (4) radical chain processes. Each method is described using examples from the recent literature.

Citing Articles

Liquid-Assisted Grinding Enables Efficient Ni-Catalyzed, Mn-Mediated Denitrogenative Cross-Electrophile Coupling of Benzotriazinones with Benzyl Chlorides.

Zhang X, Hong Y, Zou G Molecules. 2025; 30(5).

PMID: 40076285 PMC: 11901950. DOI: 10.3390/molecules30051060.

Aryl halide cross-coupling via formate-mediated transfer hydrogenation.

Cho Y, Chang Y, Quirion K, Strong Z, Dubey Z, Nguyen N Nat Chem. 2025; .

PMID: 40069564 DOI: 10.1038/s41557-024-01729-0.

One-Pot Chlorination and Cross-Electrophile Coupling of Alcohols with Aryl Chlorides.

Ahern B, Weix D Org Lett. 2025; 27(5):1164-1169.

PMID: 39853261 PMC: 11851292. DOI: 10.1021/acs.orglett.4c04676.

Palladium-Catalyzed Oxidative Allene-Allene Cross-Coupling.

Wu H, Pan Q, Grill J, Johansson M, Qiu Y, Backvall J J Am Chem Soc. 2025; 147(5):4338-4348.

PMID: 39847037 PMC: 11803718. DOI: 10.1021/jacs.4c14607.

Iron-Catalyzed Cross-Electrophile Coupling for the Formation of All-Carbon Quaternary Centers.

Pace A, Xu F, Liu W, Lavagnino M, MacMillan D J Am Chem Soc. 2024; 146(48):32925-32932.

PMID: 39568194 PMC: 11664487. DOI: 10.1021/jacs.4c14942.

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