title: Formation of ArF from LPdAr(F): catalytic conversion of aryl triflates to aryl fluorides.
abstract: Despite increasing pharmaceutical importance, fluorinated aromatic organic molecules remain difficult to synthesize. Present methods require either harsh reaction conditions or highly specialized reagents, making the preparation of complex fluoroarenes challenging. Thus, the development of general methods for their preparation that overcome the limitations of those techniques currently in use is of great interest. We have prepared [LPd(II)Ar(F)] complexes, where L is a biaryl monophosphine ligand and Ar is an aryl group, and identified conditions under which reductive elimination occurs to form an Ar-F bond. On the basis of these results, we have developed a catalytic process that converts aryl bromides and aryl triflates into the corresponding fluorinated arenes by using simple fluoride salts. We expect this method to allow the introduction of fluorine atoms into advanced, highly functionalized intermediates.
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology (MIT), Cambridge, MA 02139, USA.
authors.forename: Donald A
authors.initials: DA
authors.lastname: Watson
authors.forename: Mingjuan
authors.initials: M
authors.lastname: Su
authors.forename: Georgiy
authors.initials: G
authors.lastname: Teverovskiy
authors.forename: Yong
authors.initials: Y
authors.lastname: Zhang
authors.forename: Jorge
authors.initials: J
authors.lastname: García-Fortanet
authors.forename: Tom
authors.initials: T
authors.lastname: Kinzel
authors.forename: Stephen L
authors.initials: SL
authors.lastname: Buchwald
mesh_terms: D002384:Catalysis; D055598:Chemical Phenomena; D003287:Contrast Media; D005459:Fluorides / Q000138:chemical synthesis* / Q000737:chemistry*; D005461:Fluorine / Q000737:chemistry*; D005462:Fluorine Radioisotopes; D006845:Hydrocarbons, Fluorinated / Q000138:chemical synthesis* / Q000737:chemistry*; D007536:Isomerism; D008024:Ligands; D008698:Mesylates / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry*; D049268:Positron-Emission Tomography
chemical_list: D003287:Contrast Media; D005462:Fluorine Radioisotopes; D006845:Hydrocarbons, Fluorinated; D008024:Ligands; D008698:Mesylates; D005461:Fluorine; D010165:Palladium; D005459:Fluorides
references.citation: Chemistry. 2002 Mar 1;8(5):1006-14
references.pmid: 11891886
references.citation: J Am Chem Soc. 2006 Jun 7;128(22):7134-5
references.pmid: 16734446
references.citation: Chem Rev. 2008 May;108(5):1501-16
references.pmid: 18426240
references.citation: J Am Chem Soc. 2005 Nov 2;127(43):15304-21
references.pmid: 16248673
references.citation: Chembiochem. 2004 May 3;5(5):637-43
references.pmid: 15122635
references.citation: Angew Chem Int Ed Engl. 2008;47(32):5993-6
references.pmid: 18604865
references.citation: Chembiochem. 2004 May 3;5(5):676-84
references.pmid: 15122640
references.citation: J Am Chem Soc. 2007 Jun 27;129(25):8018-25
references.pmid: 17536798
references.citation: J Am Chem Soc. 2001 Feb 14;123(6):1232-3
references.pmid: 11456679
references.citation: J Am Chem Soc. 2008 Oct 15;130(41):13552-4
references.pmid: 18798626
references.citation: Proc Natl Acad Sci U S A. 2000 Aug 1;97(16):9226-33
references.pmid: 10922074
references.citation: J Am Chem Soc. 2004 Mar 17;126(10):3068-9
references.pmid: 15012134
references.citation: J Am Chem Soc. 2007 Feb 7;129(5):1342-58
references.pmid: 17263419
references.citation: Nat Chem. 2009 Jul;1(4):302-9
references.pmid: 21500602
references.citation: J Am Chem Soc. 2009 Mar 25;131(11):3796-7
references.pmid: 19249867
references.citation: Inorg Chem. 2008 Jan 7;47(1):5-7
references.pmid: 18052157
references.citation: Angew Chem Int Ed Engl. 2006 Apr 21;45(17):2720-5
references.pmid: 16548046
references.citation: Chembiochem. 2004 May 3;5(5):571-89
references.pmid: 15122630
references.citation: J Am Chem Soc. 2009 Jun 10;131(22):7520-1
references.pmid: 19435367
references.citation: Science. 2007 Sep 28;317(5846):1881-6
references.pmid: 17901324
references.citation: J Am Chem Soc. 2008 Aug 6;130(31):10060-1
references.pmid: 18616246
references.citation: J Am Chem Soc. 2009 Feb 11;131(5):1662-3
references.pmid: 19191693