title: Enediolate-dilithium amide mixed aggregates in the enantioselective alkylation of arylacetic acids: structural studies and a stereochemical model.
abstract: A combination of X-ray crystallography, (6)Li, (15)N, and (13)C NMR spectroscopies, and density functional theory computations affords insight into the structures and reactivities of intervening aggregates underlying highly selective asymmetric alkylations of carboxylic acid dianions (enediolates) mediated by the dilithium salt of a C2-symmetric chiral tetraamine. Crystallography shows a trilithiated n-butyllithium-dilithiated amide that has dimerized to a hexalithiated form. Spectroscopic studies implicate the non-dimerized trilithiated mixed aggregate. Reaction of the dilithiated amide with the dilithium enediolate derived from phenylacetic acid affords a tetralithio aggregate comprised of the two dianions in solution and the dimerized octalithio form in the solid state. Computational studies shed light on the details of the solution structures and afford a highly predictive stereochemical model.
authors: Department of Chemistry and Biochemistry, University of California, Santa Barbara , California 93106, United States.
authors: Yun
authors: Y
authors: Ma
authors: Craig E
authors: CE
authors: Stivala
authors: Ashley M
authors: AM
authors: Wright
authors: Trevor
authors: T
authors: Hayton
authors: Jun
authors: J
authors: Liang
authors: Ivan
authors: I
authors: Keresztes
authors: Emil
authors: E
authors: Lobkovsky
authors: David B
authors: DB
authors: Collum
authors: Armen
authors: A
authors: Zakarian
mesh_terms: D000085:Acetates / Q000737:chemistry*; D000478:Alkylation; D000577:Amides / Q000737:chemistry*; D000838:Anions / Q000737:chemistry; D018360:Crystallography, X-Ray; D019281:Dimerization; D008094:Lithium / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000085:Acetates; D000577:Amides; D000838:Anions; D009942:Organometallic Compounds; C434823:n-butyllithium; D008094:Lithium
references: J Org Chem. 2007 Aug 31;72(18):6982-91
references: 17683145
references: J Am Chem Soc. 2011 May 11;133(18):7135-51
references: 21500823
references: J Am Chem Soc. 2006 May 3;128(17):5939-48
references: 16637662
references: J Am Chem Soc. 2006 Aug 9;128(31):10326-36
references: 16881665
references: J Org Chem. 2003 Feb 21;68(4):1290-4
references: 12585867
references: J Org Chem. 2003 Apr 4;68(7):2830-8
references: 12662059
references: J Org Chem. 2007 Mar 2;72(5):1785-98
references: 17266378
references: J Am Chem Soc. 2004 May 5;126(17):5427-35
references: 15113214
references: J Org Chem. 2005 May 27;70(11):4279-83
references: 15903301
references: Dalton Trans. 2012 Feb 14;41(6):1897-902
references: 22169997
references: J Am Chem Soc. 2005 Jun 8;127(22):7968-9
references: 15926793
references: Chem Rev. 2006 Jul;106(7):2596-616
references: 16836294
references: Chem Commun (Camb). 2011 Sep 21;47(35):9915-7
references: 21811732
references: J Am Chem Soc. 2007 Mar 28;129(12):3492-3
references: 17341084
references: J Phys Chem A. 2007 Jul 26;111(29):6615-21
references: 17388388
references: J Am Chem Soc. 2010 Sep 29;132(38):13212-3
references: 20822143
references: J Org Chem. 1996 Nov 15;61(23):8103-8112
references: 11667797
references: J Am Chem Soc. 2008 May 14;130(19):6060-1
references: 18419118
references: J Am Chem Soc. 2001 Aug 22;123(33):8039-46
references: 11506560
references: Org Lett. 2002 Feb 21;4(4):573-5
references: 11843594
references: J Org Chem. 2004 Jan 9;69(1):150-7
references: 14703391
references: J Org Chem. 2012 Jul 6;77(13):5471-91
references: 22594379
references: Org Lett. 2000 Sep 7;2(18):2753-5
references: 10964357
references: Acc Chem Res. 2009 Feb 17;42(2):270-80
references: 19105594
references: J Org Chem. 2001 Sep 21;66(19):6291-8
references: 11559177
references: Angew Chem Int Ed Engl. 2006 Nov 20;45(45):7506-25
references: 17103481
references: Org Lett. 2004 Jan 22;6(2):189-92
references: 14723525
references: Chemistry. 2011 Mar 1;17(10):2996-3004
references: 21294193
references: Org Lett. 2009 May 7;11(9):1907-10
references: 19358566
references: J Org Chem. 2008 Dec 5;73(23):9426-34
references: 18973381
references: J Org Chem. 2009 Jun 19;74(12):4433-46
references: 19518150
references: Chem Rev. 2006 Jul;106(7):2734-93
references: 16836298
references: J Org Chem. 2010 Jun 4;75(11):3821-30
references: 20465266
references: J Am Chem Soc. 2005 Apr 6;127(13):4965-75
references: 15796563
references: Chem Pharm Bull (Tokyo). 1984 Sep;32(9):3428-35
references: 6525647
references: Inorg Chem. 2009 Jan 5;48(1):369-74
references: 19061386
references: J Org Chem. 2010 Dec 17;75(24):8392-9
references: 21077695
references: Inorg Chem. 1999 Nov 29;38(24):5588-5592
references: 11671287
references: J Org Chem. 2008 Dec 5;73(23):9393-402
references: 18954115
references: J Org Chem. 2001 Feb 23;66(4):1334-8
references: 11312964
references: J Org Chem. 2006 Mar 3;71(5):1837-50
references: 16496968
references: J Am Chem Soc. 2005 Mar 23;127(11):3964-72
references: 15771533
references: Org Lett. 2010 Nov 19;12(22):5124-7
references: 20886873
references: Chemistry. 2001 Aug 17;7(16):3461-5
references: 11560315
references: J Org Chem. 2005 Mar 4;70(5):1897-900
references: 15730317
references: J Org Chem. 2005 Oct 14;70(21):8298-302
references: 16209570
references: J Am Chem Soc. 2011 Aug 10;133(31):11936-9
references: 21744818
references: J Mol Model. 2006 Jan;12(2):182-9
references: 16258740
references: J Am Chem Soc. 2011 Aug 3;133(30):11492-5
references: 21721524
references: J Org Chem. 2003 Aug 8;68(16):6387-91
references: 12895075
references: J Am Chem Soc. 2002 Nov 13;124(45):13386-7
references: 12418882
references: Angew Chem Int Ed Engl. 2005 Feb 25;44(10):1448-54
references: 15724254
references: Chem Commun (Camb). 2006 Jun 4;(21):2221-3
references: 16718309
references: J Org Chem. 2005 Oct 14;70(21):8486-91
references: 16209596
references: J Mol Model. 2006 Jul;12(5):673-80
references: 16341718
references: Chem Rev. 2008 Jan;108(1):140-205
references: 18081351
references: J Org Chem. 2008 Aug 15;73(16):6086-91
references: 18646860
references: J Comput Chem. 2004 Mar;25(4):461-71
references: 14735566
references: J Am Chem Soc. 2001 Aug 22;123(33):8067-79
references: 11506563
references: J Org Chem. 1996 Jul 12;61(14):4589-4593
references: 11667384