title: A stereocontrolled synthesis of (+)-saxitoxin.
abstract: A concise stereoselective total synthesis of (+)-saxitoxin is described. A silver(I)-initiated hydroamination cascade constructs the bicyclic guanidinium ion core from a alkynyl bisguanidine. This sequence creates two C-N bonds, one C-O bond, and three rings and forms a single stereoisomer in a single synthetic transformation. This process enabled us to complete the synthesis of (+)-saxitoxin in 14 steps from N-Boc-l-serine methyl ester.
authors.affiliation: Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, USA.
authors.forename: Vasudev R
authors.initials: VR
authors.lastname: Bhonde
authors.forename: Ryan E
authors.initials: RE
authors.lastname: Looper
mesh_terms: D019791:Guanidine / Q000737:chemistry; D012530:Saxitoxin / Q000138:chemical synthesis*; D013237:Stereoisomerism
chemical_list: D012530:Saxitoxin; D019791:Guanidine
references.citation: J Physiol. 2007 Feb 15;579(Pt 1):1-14
references.pmid: 17158175
references.citation: Angew Chem Int Ed Engl. 2009;48(17):3116-20
references.pmid: 19322858
references.citation: Ann N Y Acad Sci. 1986;479:15-23
references.pmid: 3468843
references.citation: Nat Rev Neurosci. 2006 Jul;7(7):548-62
references.pmid: 16791144
references.citation: J Am Chem Soc. 2008 Sep 24;130(38):12630-1
references.pmid: 18759394
references.citation: J Am Chem Soc. 1977 Apr 13;99(8):2818-9
references.pmid: 850038
references.citation: Chem Asian J. 2009 Feb 2;4(2):277-85
references.pmid: 19040253
references.citation: Org Lett. 2010 May 7;12(9):2150-3
references.pmid: 20355743
references.citation: J Am Chem Soc. 2007 Aug 15;129(32):9964-75
references.pmid: 17658800
references.citation: Chemistry. 2011 Oct 17;17(43):12144-52
references.pmid: 21922571
references.citation: Angew Chem Int Ed Engl. 2010 Dec 3;49(49):9465-8
references.pmid: 20963737
references.citation: Org Lett. 2006 Mar 16;8(6):1073-6
references.pmid: 16524271
references.citation: Angew Chem Int Ed Engl. 2011 Jul 25;50(31):7176-8
references.pmid: 21688378
references.citation: Nat Prod Rep. 2006 Apr;23(2):200-22
references.pmid: 16572228
references.citation: Org Lett. 1999 Dec 30;1(13):2169-72
references.pmid: 10836070
references.citation: Angew Chem Int Ed Engl. 2011 Jan 17;50(3):684-7
references.pmid: 21226153
references.citation: Trends Neurosci. 2001 Aug;24(8):473-8
references.pmid: 11476887
references.citation: J Am Chem Soc. 2009 Sep 9;131(35):12524-5
references.pmid: 19678702
references.citation: J Am Chem Soc. 2006 Oct 11;128(40):13255-60
references.pmid: 17017806
references.citation: ACS Med Chem Lett. 2010 Mar 31;1(3):135-138
references.pmid: 20607120
references.citation: J Am Chem Soc. 2006 Mar 29;128(12):3926-7
references.pmid: 16551097