title: A general enantioselective route to the chamigrene natural product family.
abstract: Described in this report is an enantioselective route toward the chamigrene natural product family. The key disconnections in our synthetic approach include sequential enantioselective decarboxylative allylation and ring-closing olefin metathesis to form the all-carbon quaternary stereocenter and spirocyclic core present in all members of this class of compounds. The generality of this strategy is demonstrated by the first total syntheses of elatol and the proposed structure of laurencenone B, as well as the first enantioselective total syntheses of laurencenone C and α-chamigrene. A brief exploration of the substrate scope of the enantioselective decarboxylative allylation/ring-closing metathesis sequence with fully substituted vinyl chlorides is also presented.
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125.
authors.forename: David E
authors.initials: DE
authors.lastname: White
authors.forename: Ian C
authors.initials: IC
authors.lastname: Stewart
authors.forename: Brinton A
authors.initials: BA
authors.lastname: Seashore-Ludlow
authors.forename: Robert H
authors.initials: RH
authors.lastname: Grubbs
authors.forename: Brian M
authors.initials: BM
authors.lastname: Stoltz
references.citation: J Am Chem Soc. 2001 Jan 24;123(3):504-5
references.pmid: 11456557
references.citation: Org Lett. 2009 Jan 15;11(2):289-92
references.pmid: 19093809
references.citation: Org Lett. 2007 Jun 21;9(13):2529-31
references.pmid: 17536810
references.citation: Biofouling. 1996;10(1-3):213-24
references.pmid: 22115113
references.citation: Angew Chem Int Ed Engl. 2006 May 5;45(19):3109-12
references.pmid: 16596689
references.citation: Org Lett. 2005 Sep 15;7(19):4277-80
references.pmid: 16146406
references.citation: Org Lett. 2009 Jan 15;11(2):293-5
references.pmid: 19093836
references.citation: Org Lett. 2004 Jun 24;6(13):2229-32
references.pmid: 15200327
references.citation: J Am Chem Soc. 2007 Oct 3;129(39):11876-7
references.pmid: 17824701
references.citation: Org Lett. 2002 Jul 11;4(14):2377-80
references.pmid: 12098251
references.citation: J Am Chem Soc. 2006 Sep 6;128(35):11348-9
references.pmid: 16939246
references.citation: J Org Chem. 2007 May 25;72(11):4098-101
references.pmid: 17447815
references.citation: Angew Chem Int Ed Engl. 2009;48(20):3685-8
references.pmid: 19353600
references.citation: J Nat Prod. 2005 Nov;68(11):1677-9
references.pmid: 16309323
references.citation: J Am Chem Soc. 2009 Feb 11;131(5):1931-8
references.pmid: 19146414
references.citation: Chem Pharm Bull (Tokyo). 1990 Feb;38(2):525-8
references.pmid: 2337969
references.citation: Chem Pharm Bull (Tokyo). 1984 Aug;32(8):3047-52
references.pmid: 6518586
references.citation: Org Lett. 2006 Apr 13;8(8):1573-6
references.pmid: 16597113
references.citation: J Am Chem Soc. 2008 Jan 23;130(3):810-1
references.pmid: 18163634
references.citation: Chem Asian J. 2006 Oct 20;1(4):611-3
references.pmid: 17441100
references.citation: J Am Chem Soc. 2004 Nov 24;126(46):15044-5
references.pmid: 15547998
references.citation: Biomol Eng. 2003 Jul;20(4-6):255-9
references.pmid: 12919806
references.citation: Chem Pharm Bull (Tokyo). 2001 Jan;49(1):23-8
references.pmid: 11201220
references.citation: Org Lett. 2007 Mar 29;9(7):1339-42
references.pmid: 17343392
references.citation: J Am Chem Soc. 1986 Nov 1;108(24):7801-11
references.pmid: 22283290
references.citation: J Am Chem Soc. 2007 Aug 29;129(34):10342-3
references.pmid: 17676743
references.citation: Phytochemistry. 2005 Jan;66(2):249-60
references.pmid: 15652582
references.citation: Angew Chem Int Ed Engl. 2005 Oct 28;44(42):6924-7
references.pmid: 16206310
references.citation: Org Lett. 2003 Jul 10;5(14):2505-7
references.pmid: 12841766
references.citation: Phytochemistry. 2001 Sep;58(2):291-7
references.pmid: 11551553
references.citation: Org Lett. 2007 Apr 12;9(8):1589-92
references.pmid: 17378575
references.citation: J Nat Prod. 1997 Oct;60(10):967-70
references.pmid: 9358636
references.citation: Angew Chem Int Ed Engl. 2009;48(37):6840-3
references.pmid: 19672907
references.citation: Chem Commun (Camb). 2005 Sep 21;(35):4477-8
references.pmid: 16136256