title: Hydroxyl-substituted ladder polyethers via selective tandem epoxidation/cyclization sequence.
abstract: A new and highly selective method for the synthesis of hydroxyl-substituted tetrahydropyrans is described. This method utilizes titanium(IV) isopropoxide and diethyl tartrate to perform a diastereoselective epoxidation followed by in situ epoxide activation and highly selective endo-cyclization to form the desired tetrahydropyran ring. The HIJ ring fragment of the marine ladder polyether yessotoxin was synthesized using this two-stage tactic that proceeds with high efficiency and excellent regioselectivity.
authors: Department of Chemistry, Massachusetts Institute of Technology , 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
authors: Lara C
authors: LC
authors: Czabaniuk
authors: Timothy F
authors: TF
authors: Jamison
mesh_terms: D003500:Cyclization; D004852:Epoxy Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D004987:Ethers / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D011714:Pyrans / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D013644:Tartrates / Q000737:chemistry*
chemical_list: D004852:Epoxy Compounds; D004987:Ethers; D009942:Organometallic Compounds; D011714:Pyrans; D013644:Tartrates; C118403:tartaric acid dimethyl ether; C102815:titanium isopropoxide
references: Nat Prod Rep. 2008 Apr;25(2):401-26
references: 18389143
references: Org Lett. 2003 Jun 26;5(13):2339-42
references: 12816443
references: Angew Chem Int Ed Engl. 2009;48(29):5250-81
references: 19572302
references: Proc Natl Acad Sci U S A. 2013 Oct 15;110(42):16724-9
references: 24046369
references: Org Lett. 2003 Jun 12;5(12):2123-6
references: 12790544
references: Biochem Pharmacol. 2003 Jan 15;65(2):193-208
references: 12504795
references: J Am Chem Soc. 2009 May 20;131(19):6678-9
references: 19402635
references: Chem Soc Rev. 2009 Nov;38(11):3175-92
references: 19847350
references: J Org Chem. 1997 May 16;62(10):3183-3189
references: 11671701
references: Chemistry. 2013 Jul 22;19(30):10004-16
references: 23775936
references: Org Biomol Chem. 2011 Jun 7;9(11):3997-4006
references: 21526254
references: Angew Chem Int Ed Engl. 2008;47(38):7182-225
references: 18763702
references: Toxicon. 1985;23(3):473-9
references: 3895583
references: Science. 2007 Aug 31;317(5842):1189-92
references: 17761875
references: J Am Chem Soc. 2006 Feb 1;128(4):1056-7
references: 16433504
references: Mar Drugs. 2008;6(2):73-102
references: 18728761
references: Toxicol In Vitro. 2006 Dec;20(8):1419-26
references: 16926092
references: Nat Prod Rep. 2009 Feb;26(2):266-80
references: 19177224
references: Angew Chem Int Ed Engl. 2009;48(24):4430-2
references: 19431181
references: Chem Rev. 2005 Dec;105(12):4379-405
references: 16351048
references: Mar Drugs. 2010;8(3):763-809
references: 20411125
references: Angew Chem Int Ed Engl. 2008;47(42):8055-8
references: 18785198
references: Biochem Pharmacol. 2001 Apr 1;61(7):827-33
references: 11274968
references: J Am Chem Soc. 2009 May 13;131(18):6383-5
references: 19385615
references: Toxicon. 1990;28(9):1095-104
references: 2260107
references: Chem Rev. 2005 Dec;105(12):4314-47
references: 16351046
references: Chemistry. 2002 Oct 4;8(19):4346-53
references: 12355522