Reevaluation of the mechanism of the amination of aryl halides catalyzed by BINAP-ligated palladium complexes

Journal of the American Chemical Society
Shashank ShekharStephen L Buchwald

Abstract

Two previous mechanistic studies of the amination of aryl halides catalyzed by palladium complexes of 1,1'-binaphthalene-2,2'-diylbis(diphenylphosphine) (BINAP) are reexamined by the authors of both studies. This current work includes a detailed study of the identity of the BINAP-ligated palladium complexes present in reactions of amines with aryl halides and rate measurements of these catalytic reactions initiated with pure precatalysts and precatalysts generated in situ from [Pd2(dba)3] and BINAP. This work reveals errors in both previous studies, and we describe our current state of understanding of the mechanism of this synthetically important transformation. 31P NMR spectroscopy shows that several palladium(0) species are present in the catalytic system when the catalyst is generated in situ from [Pd2(dba)3] and BINAP, and that at least two of these complexes generate catalytic intermediates. Further, these spectroscopic studies and accompanying kinetic data demonstrate that an apparent positive order in the concentration of amine during reactions of secondary amines is best attributed to catalyst decomposition. Kinetic studies with isolated precatalysts show that the rates of the catalytic reactions are independent of the...Continue Reading

Citations

Aug 11, 2010·Journal of the American Chemical Society·Jessica L Klinkenberg, John F Hartwig
Feb 24, 2011·Journal of the American Chemical Society·Asa D MelhadoF Dean Toste
Apr 25, 2012·Journal of the American Chemical Society·Raffaele CredendinoLuigi Cavallo
Feb 20, 2010·Journal of the American Chemical Society·Baoguo ZhaoYian Shi
Apr 23, 2011·The Journal of Organic Chemistry·Shashank ShekharSteven C Cullen
Aug 2, 2012·The Journal of Organic Chemistry·Pengju JiMichael I Page
Jun 4, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Robert A GossageBrian F Yates
May 8, 2009·Chemical Society Reviews·Mandy-Nicole BirkholzPiet W N M van Leeuwen
May 8, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Alexandra K de K LewisPeter B Hitchcock
Mar 5, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Jason A GillespiePaul C J Kamer
Oct 22, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Claire L McMullinNatalie Fey
Oct 29, 2014·Journal of the American Chemical Society·Garima Jindal, Raghavan B Sunoj
Aug 19, 2015·Journal of the American Chemical Society·Donna G Blackmond
May 9, 2008·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Ibrahim Mustafa El-DeebSo Ha Lee
Feb 7, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Song-Lin ZhangLi-Jun Sun
Jul 13, 2018·Chemical Communications : Chem Comm·Connor J ThomsonDavid O'Hagan
Aug 13, 2014·Chemistry : a European Journal·Mélanie PlatonJean-Cyrille Hierso
Sep 23, 2006·Chemistry : a European Journal·Asma TougertiAnny Jutand
Jan 29, 2008·Chemistry : a European Journal·Michael G OrganCory Valente
Feb 22, 2008·Chemistry : a European Journal·Markus R an der HeidenHuub C J Hoefsloot
Jul 30, 2008·Angewandte Chemie·David S Surry, Stephen L Buchwald
Nov 28, 2009·Angewandte Chemie·Jinling HeNoritaka Mizuno
Sep 30, 2010·Chemical Society Reviews·Yoann AubinJean-Luc Renaud
May 19, 2011·Chemistry : a European Journal·Chun-Hong TangKang-Nian Fan
Dec 14, 2006·Organic & Biomolecular Chemistry·Jonathan P Knowles, Andrew Whiting
Nov 1, 2011·Chemical Communications : Chem Comm·Holm Petzold, Albara I S Alrawashdeh
Jun 6, 2019·Angewandte Chemie·Ruth DorelAlexander M Haydl

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