title: Hydroxyproline-derived pseudoenantiomeric [2.2.1] bicyclic phosphines: asymmetric synthesis of (+)- and (-)-pyrrolines.
abstract: We have prepared two new diastereoisomeric 2-aza-5-phosphabicyclo[2.2.1]heptanes from naturally occurring trans-4-hydroxy-L-proline in six chemical operations. These syntheses are concise and highly efficient, with straightforward purification. When we used these chiral phosphines as catalysts for reactions of γ-substituted allenoates with imines, we obtained enantiomerically enriched pyrrolines in good yields with excellent enantioselectivities. These two diastereoisomeric phosphines functioned as pseudoenantiomers, providing their chiral pyrrolines with opposite absolute configurations.
authors.affiliation: Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095-1569, United States.
authors.forename: Christopher E
authors.initials: CE
authors.lastname: Henry
authors.forename: Qihai
authors.initials: Q
authors.lastname: Xu
authors.forename: Yi Chiao
authors.initials: YC
authors.lastname: Fan
authors.forename: Tioga J
authors.initials: TJ
authors.lastname: Martin
authors.forename: Lee
authors.initials: L
authors.lastname: Belding
authors.forename: Travis
authors.initials: T
authors.lastname: Dudding
authors.forename: Ohyun
authors.initials: O
authors.lastname: Kwon
mesh_terms: D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D006909:Hydroxyproline / Q000737:chemistry*; D015394:Molecular Structure; D010720:Phosphines / Q000138:chemical synthesis* / Q000737:chemistry; D011758:Pyrroles / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D001643:Bridged Bicyclo Compounds; D010720:Phosphines; D011758:Pyrroles; C013231:pyrroline; D006909:Hydroxyproline
references.citation: Chem Soc Rev. 2008 Jun;37(6):1140-52
references.pmid: 18497927
references.citation: Angew Chem Int Ed Engl. 2012 Jan 16;51(3):767-70
references.pmid: 22162303
references.citation: Acc Chem Res. 2006 Aug;39(8):520-30
references.pmid: 16906748
references.citation: Acc Chem Res. 2001 Jul;34(7):535-44
references.pmid: 11456471
references.citation: Chem Commun (Camb). 2013 Dec 25;49(99):11588-619
references.pmid: 24196409
references.citation: BMC Cancer. 2013 Apr 22;13:198
references.pmid: 23607551
references.citation: J Am Chem Soc. 2008 Oct 29;130(43):14030-1
references.pmid: 18834118
references.citation: Org Lett. 2006 Aug 17;8(17):3643-6
references.pmid: 16898781
references.citation: J Am Chem Soc. 2011 Feb 16;133(6):1726-9
references.pmid: 21226456
references.citation: Chem Soc Rev. 2014 May 7;43(9):2927-40
references.pmid: 24663290
references.citation: Angew Chem Int Ed Engl. 2013 May 3;52(19):5115-9
references.pmid: 23580259
references.citation: J Biol Chem. 2008 Apr 11;283(15):9571-9
references.pmid: 18230616
references.citation: Chem Sci. 2012 Jan 1;3(8):2510-2514
references.pmid: 22798981
references.citation: Angew Chem Int Ed Engl. 2006 Feb 20;45(9):1426-9
references.pmid: 16444787
references.citation: J Org Chem. 2005 Nov 25;70(24):9975-84
references.pmid: 16292830
references.citation: J Am Chem Soc. 2008 Apr 30;130(17):5660-1
references.pmid: 18393504
references.citation: Org Lett. 2001 Dec 27;3(26):4295-8
references.pmid: 11784201
references.citation: J Am Chem Soc. 2007 Sep 12;129(36):10988-9
references.pmid: 17711278
references.citation: Mol Cancer Ther. 2009 May;8(5):1218-26
references.pmid: 19417142
references.citation: J Am Chem Soc. 2011 Aug 10;133(31):12293-7
references.pmid: 21766794
references.citation: Chem Commun (Camb). 2012 Mar 14;48(22):2764-6
references.pmid: 22310936
references.citation: J Am Chem Soc. 2007 May 9;129(18):5843-5
references.pmid: 17439124
references.citation: Chem Commun (Camb). 2012 Feb 7;48(12):1724-32
references.pmid: 22073396
references.citation: Angew Chem Int Ed Engl. 2010 Jun 14;49(26):4467-70
references.pmid: 20480471
references.citation: Chem Rev. 2002 May;102(5):1669-730
references.pmid: 11996547
references.citation: Chemistry. 2012 Jan 2;18(1):76-9
references.pmid: 22162097
references.citation: Chem Soc Rev. 2009 Nov;38(11):3102-16
references.pmid: 19847345
references.citation: Acc Chem Res. 2010 Jul 20;43(7):1005-18
references.pmid: 20232829