The Hydroarylation Reaction—Scope and Limitations

Molecules

Jan C. Namyslo¹  Jörg Storsberg¹  Jens Klinge¹  Christian Gärtner¹  Min-Liang Yao¹  Nuket Ocal¹ 

[1] ¹Institute of Organic Chemistry, Clausthal University of Technology, Leibnizstr. 6, D-38678 Clausthal-Zellerfeld, Germany ²Department of Chemistry, Faculty of Arts and Sciences, Davutpasa Campus, Yildiz Technical University, 34210 Esenler-Istanbul, Turkey

关键词: homogenous catalysis;    palladium;    C-C coupling;    domino reaction;    rearrangement;    mechanism;   

DOI  :  10.3390/molecules15053402

来源: mdpi

【 摘 要 】

The synthetic potential of stereoselective, palladium-catalyzed hydro(het)arylation reactions of bi-, tri- and tetracyclic (hetero)alkenes in the presence of phospines and arsines as highly efficient ligands was studied. The mechanism of this reductive Heck reaction becomes more complex in the case of benzonorbornenes. Hydroarylation of diazabicyclo-[2.2.1]heptenes provides a stereoselective access to aryldiaminocyclopentanes. Electron-deficient arylpalladium complexes shift the reaction towards the product of a formal 1,2-hydrazidoarylation reaction of 1,3-cyclopentadiene by a stereoselective C-N cleavage. Due to steric reasons, rigid bicyclo[2.2.2]octenes react slower in hydroarylation reactions than the corresponding bicyclo[2.2.1]heptenes. The more flexible bicyclo[4.2.2]decene system already tends to undergo domino-Heck reactions, even under reductive conditions. When a tetracyclic cis-allylcyclopropane is carbopalladated in the presence of formates, the neighboring cyclopropane ring is attacked in the first reported example of a π,σ domino-Heck reaction.

【 授权许可】

CC BY   
This is an open access article distributed under the Creative Commons Attribution License (CC BY) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.