title: Stereoselective synthesis of quaternary carbons via the dianionic Ireland-Claisen rearrangement.
abstract: A dianionic Ireland-Claisen rearrangement of chiral, nonracemic α-methyl-β-hydroxy allylic esters has been developed that proceeds with high diastereoselectivity and provides products containing three contiguous stereogenic carbons, including a quaternary center. The potential utility of the rearrangement for complex molecule synthesis is also demonstrated.
authors.affiliation: Kenan, Caudill, Murray and Venable Laboratories of Chemistry University of North Carolina at Chapel Hill , Chapel Hill, North Carolina 27599, United States.
authors.forename: Michael T
authors.initials: MT
authors.lastname: Crimmins
authors.forename: John D
authors.initials: JD
authors.lastname: Knight
authors.forename: Philip S
authors.initials: PS
authors.lastname: Williams
authors.forename: Yan
authors.initials: Y
authors.lastname: Zhang
mesh_terms: D000838:Anions / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D004952:Esters; D015394:Molecular Structure; D011422:Propionates / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000838:Anions; D004952:Esters; D011422:Propionates; D002244:Carbon
references.citation: J Org Chem. 2001 Feb 9;66(3):894-902
references.pmid: 11430110
references.citation: Chem Rev. 2008 Dec;108(12):5278-98
references.pmid: 18942794
references.citation: Org Lett. 2000 Mar 23;2(6):775-7
references.pmid: 10754681
references.citation: J Am Chem Soc. 2009 Jul 1;131(25):9038-45
references.pmid: 19485326
references.citation: Tetrahedron Lett. 2011 Apr 27;52(17):2120-2123
references.pmid: 21528009
references.citation: J Am Chem Soc. 2004 Aug 25;126(33):10264-6
references.pmid: 15315437
references.citation: J Org Chem. 2004 Jun 11;69(12):4185-91
references.pmid: 15176847
references.citation: Org Lett. 2010 Nov 5;12(21):5028-31
references.pmid: 20936859
references.citation: Chem Rev. 2004 Jun;104(6):2939-3002
references.pmid: 15186185
references.citation: Org Lett. 2014 Apr 4;16(7):1956-9
references.pmid: 24673388
references.citation: Org Lett. 1999 Dec 16;1(12):2029-32
references.pmid: 10836060
references.citation: J Org Chem. 2002 Dec 13;67(25):8871-6
references.pmid: 12467401