title: Assignment of the structure of petrocortyne A by mixture syntheses of four candidate stereoisomers.
abstract: Two different mixture synthesis routes have been used to make the four stereoisomers of petrocortyne A. A first quick and dirty route provided a mixture of the four isomers in nonselective fashion. Mosher and 2-naphthylmethoxyacetic acid (NMA) ester methods were developed to identify the components, and the mixture was partially resolved on analytical chiral HPLC to give the two pure enantiomers of petrocortyne A and the racemate of its diastereomer. A second fluorous mixture synthesis produced all four isomers of petrocortyne A in individual pure form. Comparison of spectra of Mosher derivatives of the synthetic isomers with two supposedly different natural products showed that both natural samples were instead identical and had the (3S,14S) configuration. Likewise, petrocortynes B, D, and F-H are (3S,14S) and petrocortyne D is (3R,14S). Having access to all possible candidate isomers of both petrocortyne A and its Mosher derivatives provided a secure structure assignment not so much because one of the isomers matched the natural product, but because all of the other isomers did not.
authors.affiliation: Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA.
authors.forename: Bin
authors.initials: B
authors.lastname: Sui
authors.forename: Edmund A-H
authors.initials: EA
authors.lastname: Yeh
authors.forename: Dennis P
authors.initials: DP
authors.lastname: Curran
mesh_terms: D000085:Acetates / Q000737:chemistry; D000818:Animals; D001688:Biological Products / Q000138:chemical synthesis*; D004952:Esters / Q000737:chemistry; D005233:Fatty Alcohols / Q000138:chemical synthesis*; D015394:Molecular Structure; D047130:Petrosia / Q000737:chemistry*; D010648:Phenylacetates / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000085:Acetates; D001688:Biological Products; D004952:Esters; D005233:Fatty Alcohols; D010648:Phenylacetates; C487015:petrocortyne A; C108322:Mosher's acid; C013598:methoxyacetic acid
references.citation: J Nat Prod. 1999 Apr;62(4):554-9
references.pmid: 10217707
references.citation: J Am Chem Soc. 2009 Apr 22;131(15):5411-3
references.pmid: 19323551
references.citation: Angew Chem Int Ed Engl. 1998 Aug 17;37(15):1986-2012
references.pmid: 29711061
references.citation: Nat Protoc. 2007;2(10):2451-8
references.pmid: 17947986
references.citation: J Nat Prod. 2001 Jan;64(1):46-53
references.pmid: 11170665
references.citation: Angew Chem Int Ed Engl. 2008;47(6):1130-3
references.pmid: 18175302
references.citation: Science. 2001 Mar 2;291(5509):1766-9
references.pmid: 11230688
references.citation: Chem Soc Rev. 2005 Apr;34(4):355-65
references.pmid: 15778769
references.citation: Org Lett. 2002 Nov 14;4(23):4143-6
references.pmid: 12423107
references.citation: Chem Rev. 2005 Dec;105(12):4237-313
references.pmid: 16351045
references.citation: Nat Prod Rep. 2006 Feb;23(1):26-78
references.pmid: 16453031
references.citation: J Nat Prod. 2001 Dec;64(12):1565-7
references.pmid: 11754614
references.citation: Angew Chem Int Ed Engl. 2006 Apr 3;45(15):2423-6
references.pmid: 16526090
references.citation: Org Lett. 2007 Aug 2;9(16):3001-4
references.pmid: 17616200
references.citation: Science. 1998 Dec 18;282(5397):2247-50
references.pmid: 9856945
references.citation: J Am Chem Soc. 2006 Jul 26;128(29):9561-73
references.pmid: 16848495
references.citation: Chemistry. 2005 Aug 19;11(17):4866-80
references.pmid: 15915521
references.citation: Org Lett. 2010 Apr 16;12(8):1768-71
references.pmid: 20337423
references.citation: J Am Chem Soc. 2006 Aug 2;128(30):9943-56
references.pmid: 16866554
references.citation: Naunyn Schmiedebergs Arch Pharmacol. 2003 Dec;368(6):448-56
references.pmid: 14615882
references.citation: J Nat Prod. 1999 Sep;62(9):1215-7
references.pmid: 10514299
references.citation: J Nat Prod. 1998 Oct;61(10):1268-73
references.pmid: 9784165
references.citation: Adv Synth Catal. 2009 May 1;351(7-8):1035-1040
references.pmid: 20160880
references.citation: Cancer Lett. 2002 Nov 8;185(1):95-101
references.pmid: 12142084
references.citation: European J Org Chem. 2008 Oct 1;2008(28):4790-4795
references.pmid: 23519828