Copper-Mediated C-N Coupling of Arylsilanes with Nitrogen Nucleophiles.
A method for the oxidative coupling of arylsilanes with nitrogen nucleophiles is reported. This method occurs with a broad range of heptamethyltrisiloxylarenes and nitrogen nucleophiles, proceeds with the arylsilane as limiting reagent, and does not require a fluoride activator with electron-poor arylsilanes. The combination of this method with C-H silylation generates arylamines from unactivated arenes with site selectivity controlled by steric effects. This combination of steps gives direct access to many compounds that cannot be accessed via alternative C-H functionalization methods, including direct C-H amination or the combination of C-H borylation and amination.
Department of Chemistry, University of California , Berkeley, California 94720, United States.
Johannes
J
Morstein
Department of Chemistry, University of California , Berkeley, California 94720, United States.
Eric D
ED
Kalkman
Christian
C
Bold
Department of Chemistry, University of California , Berkeley, California 94720, United States.
Chen
C
Cheng
Department of Chemistry, University of California , Berkeley, California 94720, United States.
John F
JF
Hartwig
D000586:Amination; D000588:Amines / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry; D012821:Silanes / Q000737:chemistry*; D012969:Sodium Fluoride / Q000737:chemistry
D000588:Amines; D009942:Organometallic Compounds; D012821:Silanes; C015092:cupric acetate; D003300:Copper; D012969:Sodium Fluoride
Science. 2014 Feb 21;343(6173):853-7
24558154
Acc Chem Res. 2008 Nov 18;41(11):1534-44
18681463
J Med Chem. 2013 Jan 24;56(2):388-405
23061607
Angew Chem Int Ed Engl. 2016 Jul 4;55(28):8054-7
27214849
Bioorg Med Chem Lett. 2008 Mar 15;18(6):1939-44
18291645
J Org Chem. 2016 May 6;81(9):3942-50
27045570
Org Lett. 2007 Mar 1;9(5):761-4
17274622
Org Process Res Dev. 2015;19(8):982-994
26478695
J Am Chem Soc. 2009 Apr 15;131(14):5044-5
19309072
Beilstein J Org Chem. 2011 Jan 14;7:59-74
21286396
Org Biomol Chem. 2009 Mar 7;7(5):869-73
19225669
J Am Chem Soc. 2015 Jan 21;137(2):592-5
25514197
Science. 2016 Sep 9;353(6304):1144-7
27609890
Science. 2015 Sep 18;349(6254):1326-30
26383949
Acc Chem Res. 2008 Nov 18;41(11):1486-99
18681465
Chem Rev. 2015 Sep 9;115(17):8946-75
25714857