Palladium-Catalyzed Homocoupling of Highly Fluorinated Arylboronates: Studies of the Influence of Strongly vs Weakly Coordinating Solvents on the Reductive Elimination Process

Journal of the American Chemical Society
Yudha P BudimanTodd B Marder

Abstract

C-C reductive elimination from [PdL2(C6F5)2] to form polyfluorinated biaryls has been a challenge for over 50 years. Thus, palladium-catalyzed homocoupling of arylboronates (ArF-Bpin) containing two ortho-fluorine substituents is very difficult, as the reaction typically stops at the [PdL2(ArF)2] stage after two transmetalation steps. The transmetalated complexes cis-[Pd(MeCN)2(C6F5)2] (3a), cis-[Pd(MeCN)2(2,4,6-C6F3H2)2] (3b), and cis-[Pd(MeCN)2(2,6-C6F2H3)2] (3e) have been isolated from the reaction of ArF-Bpin with Pd(OAc)2 in acetonitrile solvent, with no homocoupling observed. However, catalytic homocoupling proceeds smoothly in a "weakly coordinating" arene solvent as long as no ancillary ligands or coordinating solvents are present. DFT computations reveal that the active catalyst formed by arene solvent coordination leads to an overall reduced barrier for the reductive elimination step compared to the formation of stable [PdL2(ArF)2] complexes in the presence of a donor ligand or solvent L.

References

Oct 21, 2005·Organic Letters·Toshinobu KorenagaTakashi Sakai
May 25, 2006·Journal of the American Chemical Society·Carlo AdamoHakim Lakmini
Jun 17, 2006·The Journal of Organic Chemistry·Jinu S MathewDonna G Blackmond
Jul 12, 2008·Chemical Reviews·Jean-Marc WeibelPatrick Pale
Jul 24, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Take-aki KoizumiTakakazu Yamamoto
Feb 24, 2009·Journal of the American Chemical Society·Martín Pérez-RodríguezPablo Espinet
Aug 28, 2009·Journal of the American Chemical Society·Meagan E EvansWilliam D Jones
Apr 27, 2010·Chemical Society Reviews·Liqin Xue, Zhenyang Lin
May 8, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·José RuizChristoph Janiak
Jun 26, 2010·Science·Eun Jin ChoStephen L Buchwald
Jul 1, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Irene AraHelvia Miedes
Dec 22, 2010·Organic Letters·Hu LiZhang-Jie Shi
Sep 20, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Raúl Díaz-Torres, Santiago Alvarez
Jul 16, 2013·Accounts of Chemical Research·Max García-MelchorFeliu Maseras
Jan 17, 2014·Chemistry : a European Journal·Masato OhashiSensuke Ogoshi
May 23, 2015·Acta Crystallographica. Section E, Crystallographic Communications·Ricarda HeckelEdwin Weber
Apr 14, 2009·Journal of Chemical Theory and Computation·Mariusz P MitorajTom Ziegler
Sep 17, 2016·Angewandte Chemie·Estefanía GioriaPablo Espinet
Jan 18, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Carleen CullinaneAxel Klein

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Citations

Nov 17, 2020·Chemistry : a European Journal·Yudha P BudimanTodd B Marder
Nov 27, 2020·Chemistry : a European Journal·Steffen A FöhrenbacherUdo Radius
Feb 7, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Ashok Kakkar
Oct 1, 2021·Chemical Communications : Chem Comm·Jaime Ponce-de-León, Pablo Espinet
Oct 8, 2021·Chemical Reviews·Shubhankar Kumar BoseTodd B Marder

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