title: Activation of alcohols with carbon dioxide: intermolecular allylation of weakly acidic pronucleophiles.
abstract: The direct coupling of allyl alcohols with nitroalkanes, nitriles, and aldehydes using catalytic Pd(PPh3)4 has been accomplished via activation of C-OH bonds with CO2. The in situ formation of carbonates from alcohols and CO2 facilitates oxidative addition to Pd to form reactive π-allylpalladium intermediates. In addition, the formation of a strong base activates nucleophiles toward the reaction with the π-allylpalladium electrophile. Overall, this atom economical reaction provides a new C-C bond without the use of an external base and generates water as the only byproduct.
authors.affiliation: Department of Chemistry, The University of Kansas , 2010 Malott Hall, 1251 Wescoe Hall Drive, Lawrence, Kansas 66045, United States.
authors.forename: Simon B
authors.initials: SB
authors.lastname: Lang
authors.forename: Theresa M
authors.initials: TM
authors.lastname: Locascio
authors.forename: Jon A
authors.initials: JA
authors.lastname: Tunge
references.citation: Chem Commun (Camb). 2010 Dec 7;46(45):8662-4
references.pmid: 20953486
references.citation: Org Lett. 2003 Sep 4;5(18):3241-4
references.pmid: 12943397
references.citation: Science. 2013 May 31;340(6136):1065-8
references.pmid: 23723229
references.citation: Angew Chem Int Ed Engl. 2000 Feb;39(4):802-804
references.pmid: 10760875
references.citation: J Am Chem Soc. 2014 Feb 26;136(8):3020-3
references.pmid: 24506196
references.citation: J Am Chem Soc. 2001 Oct 24;123(42):10401-2
references.pmid: 11603997
references.citation: Org Lett. 2010 Jun 18;12(12):2726-9
references.pmid: 20469923
references.citation: J Am Chem Soc. 2011 Sep 21;133(37):14785-94
references.pmid: 21830777
references.citation: J Am Chem Soc. 2011 Mar 23;133(11):3732-5
references.pmid: 21355548
references.citation: Science. 2006 Apr 7;312(5770):67-72
references.pmid: 16601184
references.citation: Chem Soc Rev. 2012 Jun 21;41(12):4467-83
references.pmid: 22576362
references.citation: J Am Chem Soc. 2007 Apr 11;129(14):4138-9
references.pmid: 17371027
references.citation: Org Lett. 2004 Oct 28;6(22):4085-8
references.pmid: 15496105
references.citation: Org Lett. 2008 Mar 20;10(6):1207-10
references.pmid: 18302396
references.citation: Angew Chem Int Ed Engl. 2009;48(20):3648-52
references.pmid: 19360820
references.citation: J Org Chem. 1997 Apr 18;62(8):2662-2664
references.pmid: 11671618
references.citation: Org Lett. 2009 Dec 17;11(24):5630-3
references.pmid: 19921827
references.citation: J Org Chem. 2004 Apr 2;69(7):2595-7
references.pmid: 15049667
references.citation: Science. 2009 Dec 18;326(5960):1690-4
references.pmid: 19965381
references.citation: J Am Chem Soc. 2006 May 17;128(19):6314-5
references.pmid: 16683785
references.citation: J Am Chem Soc. 2007 Jun 20;129(24):7508-9
references.pmid: 17523648
references.citation: Angew Chem Int Ed Engl. 2011 Sep 26;50(40):9471-4
references.pmid: 21915965
references.citation: Acc Chem Res. 2003 Apr;36(4):255-63
references.pmid: 12693923
references.citation: J Am Chem Soc. 2007 Sep 19;129(37):11336-7
references.pmid: 17715928
references.citation: Org Lett. 2009 Mar 19;11(6):1453-6
references.pmid: 19243116
references.citation: J Org Chem. 1999 Jul 9;64(14):5000-5001
references.pmid: 34237872
references.citation: J Am Chem Soc. 2002 Sep 18;124(37):10968-9
references.pmid: 12224930