Electrosynthesis as a Powerful Method for the Generation of Catalytic Intermediates: Efficient Isolation of a Palladium Aryl Halide Oxidative Addition Product

✍ Scribed by Dr. Veronika A. Zinovyeva; Caihong Luo; Sophie Fournier; Dr. Charles H. Devillers; Dr. Hélène Cattey; Dr. Henri Doucet; Prof. Dr. Jean-Cyrille Hierso; Prof. Dr. Dominique Lucas

• Book ID: 102795953
• Publisher: John Wiley and Sons
• Year: 2011
• Tongue: English
• Weight: 521 KB
• Volume: 17
• Category: Article
• ISSN: 0947-6539
• DOI: 10.1002/chem.201100629

✦ Synopsis

Dedicated to Professor Yves Mugnier for his contribution to the development of electrochemistry in organometallic synthesis

Electrosynthesis has become a useful and commonly used technique in organic chemistry. [1] Conversely, its use is still limited in organometallic synthesis, [2] despite its potential to control at the finest level, through electron transfer, elementary steps of important metal-mediated transformations. [3] This lack of popularity partly originates in the potential difficulty in separating the reaction products from the supporting electrolyte. Yet, in the vast majority of cases the separation can be readily achieved in many practical ways such as selective precipitation, solid-liquid or liquid-liquid extraction, and even sometimes column chromatography. [4] Electrochemical studies have greatly contributed to the mechanistic understanding of catalytic cross-coupling reactions, for instance by employing valuable analytical methods to investigate features of [(Pd 0 ,Pd II )/phosphane(s)] active organometallic catalysts. [5] In general, in mechanistic investigations the isolation and characterization of catalytic intermediates is of crucial importance. In this purpose, various chemical methods have been employed, which allow forming model compounds of aryl halides oxidative addition on palladium species stabilized by chelating diphosphanes or several monophosphanes. [6a, 7] As illustrated in Scheme 1, both the trans-ligation on preformed [Pd II