title: Insights into directing group ability in palladium-catalyzed C-H bond functionalization.
abstract: This paper describes a detailed investigation of factors controlling the dominance of a directing group in Pd-catalyzed ligand-directed arene acetoxylation. Mechanistic studies, involving reaction kinetics, Hammett analysis, kinetic isotope effect experiments, and the kinetic order in oxidant, have been conducted for a series of different substrates. Initial rates studies of substrates bearing different directing groups showed that these transformations are accelerated by the use of electron-withdrawing directing groups. However, in contrast, under conditions where two directing groups are in competition with one another in the same reaction flask, substrates with electron-donating directing groups react preferentially. These results are discussed in the context of the proposed mechanism for Pd-catalyzed arene acetoxylation.
authors.affiliation: Chemistry Department, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, USA.
authors.forename: Lopa V
authors.initials: LV
authors.lastname: Desai
authors.forename: Kara J
authors.initials: KJ
authors.lastname: Stowers
authors.forename: Melanie S
authors.initials: MS
authors.lastname: Sanford
mesh_terms: D000577:Amides / Q000737:chemistry; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D004791:Enzyme Inhibitors / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry*; D007700:Kinetics; D015394:Molecular Structure; D010091:Oximes / Q000737:chemistry; D010165:Palladium / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry
chemical_list: D000577:Amides; D004791:Enzyme Inhibitors; D010091:Oximes; D011725:Pyridines; D010165:Palladium; D002244:Carbon; D006859:Hydrogen
references.citation: J Am Chem Soc. 2006 Dec 27;128(51):16496-7
references.pmid: 17177387
references.citation: Org Lett. 2006 Jul 20;8(15):3391-4
references.pmid: 16836413
references.citation: Org Lett. 2005 Sep 15;7(19):4149-52
references.pmid: 16146374
references.citation: Inorg Chem. 2006 Dec 25;45(26):11060-8
references.pmid: 17173466
references.citation: J Am Chem Soc. 2005 Mar 30;127(12):4156-7
references.pmid: 15783182
references.citation: Chem Rev. 2007 Nov;107(11):5318-65
references.pmid: 17973536
references.citation: Bioorg Med Chem. 2002 Jul;10(7):2381-6
references.pmid: 11983535
references.citation: J Am Chem Soc. 2006 Jul 12;128(27):8754-6
references.pmid: 16819868
references.citation: J Am Chem Soc. 2003 Oct 8;125(40):12084-5
references.pmid: 14518981
references.citation: J Am Chem Soc. 2005 Oct 26;127(42):14560-1
references.pmid: 16231894
references.citation: Org Lett. 2007 Apr 12;9(8):1449-51
references.pmid: 17358073
references.citation: J Am Chem Soc. 2006 Jul 19;128(28):9048-9
references.pmid: 16834374
references.citation: J Am Chem Soc. 2004 Mar 3;126(8):2300-1
references.pmid: 14982422
references.citation: Chem Rev. 2002 May;102(5):1731-70
references.pmid: 11996548
references.citation: Angew Chem Int Ed Engl. 2007;46(29):5554-8
references.pmid: 17579890
references.citation: J Am Chem Soc. 2005 Oct 12;127(40):13754-5
references.pmid: 16201772
references.citation: Angew Chem Int Ed Engl. 2005 Dec 1;44(45):7420-4
references.pmid: 16247822
references.citation: J Am Chem Soc. 2007 Nov 28;129(47):14570-1
references.pmid: 17985911
references.citation: Angew Chem Int Ed Engl. 2005 Jun 27;44(26):4046-8
references.pmid: 15912550
references.citation: J Am Chem Soc. 2002 Feb 27;124(8):1586-7
references.pmid: 11853427
references.citation: J Am Chem Soc. 2006 Jun 7;128(22):7134-5
references.pmid: 16734446
references.citation: J Am Chem Soc. 2006 Nov 1;128(43):14047-9
references.pmid: 17061885
references.citation: Angew Chem Int Ed Engl. 2005 Mar 29;44(14):2112-5
references.pmid: 15729724
references.citation: J Am Chem Soc. 2005 May 25;127(20):7330-1
references.pmid: 15898779
references.citation: J Am Chem Soc. 2006 Jan 18;128(2):581-90
references.pmid: 16402846
references.citation: Org Lett. 2006 Mar 16;8(6):1141-4
references.pmid: 16524288
references.citation: J Am Chem Soc. 2006 Feb 1;128(4):1066-7
references.pmid: 16433509
references.citation: J Am Chem Soc. 2005 Sep 21;127(37):12790-1
references.pmid: 16159259
references.citation: J Org Chem. 2006 Aug 4;71(16):5951-8
references.pmid: 16872177
references.citation: Science. 2007 May 25;316(5828):1172-5
references.pmid: 17525334
references.citation: J Am Chem Soc. 2006 Oct 4;128(39):12634-5
references.pmid: 17002342
references.citation: J Am Chem Soc. 2007 Mar 28;129(12):3510-1
references.pmid: 17335217
references.citation: J Am Chem Soc. 2007 Oct 3;129(39):11904-5
references.pmid: 17845047
references.citation: Org Lett. 2005 Aug 18;7(17):3657-9
references.pmid: 16092843
references.citation: Chem Rev. 2007 Jan;107(1):174-238
references.pmid: 17212475
references.citation: J Am Chem Soc. 2004 Jul 21;126(28):8658-9
references.pmid: 15250711
references.citation: J Am Chem Soc. 2005 Sep 28;127(38):13154-5
references.pmid: 16173737
references.citation: Chemistry. 2001 Jun 1;7(11):2341-8
references.pmid: 11446637
references.citation: Angew Chem Int Ed Engl. 1999 Jun 14;38(12):1698-1712
references.pmid: 29711186
references.citation: J Am Chem Soc. 2008 Mar 19;130(11):3304-6
references.pmid: 18298118
references.citation: J Am Chem Soc. 2006 Jan 11;128(1):78-9
references.pmid: 16390130
references.citation: J Am Chem Soc. 2004 Aug 4;126(30):9186-7
references.pmid: 15281800
references.citation: Org Lett. 2006 Jul 20;8(15):3387-90
references.pmid: 16836412
references.citation: Dalton Trans. 2006 Apr 14;(14):1768-75
references.pmid: 16568186
references.citation: Org Lett. 2007 Jul 19;9(15):2931-4
references.pmid: 17595097
references.citation: J Am Chem Soc. 2006 Jun 14;128(23):7416-7
references.pmid: 16756276
references.citation: Org Biomol Chem. 2006 Nov 21;4(22):4041-7
references.pmid: 17312954
references.citation: J Am Chem Soc. 2007 Jun 20;129(24):7666-73
references.pmid: 17530847
references.citation: Org Lett. 2006 Jun 8;8(12):2523-6
references.pmid: 16737304
references.citation: J Am Chem Soc. 2001 Aug 22;123(33):8149-50
references.pmid: 11506585
references.citation: J Am Chem Soc. 2004 Aug 11;126(31):9542-3
references.pmid: 15291549
references.citation: J Am Chem Soc. 2007 Aug 15;129(32):9879-84
references.pmid: 17649995
references.citation: J Am Chem Soc. 2004 Nov 10;126(44):14342-3
references.pmid: 15521739