title: Synthetic Strategies toward Natural Products Containing Contiguous Stereogenic Quaternary Carbon Atoms.
abstract: Strategies for the total synthesis of complex natural products that contain two or more contiguous stereogenic quaternary carbon atoms in their intricate structures are reviewed with 12 representative examples. Emphasis has been put on methods to create quaternary carbon stereocenters, including syntheses of the same natural product by different groups, thereby showcasing the diversity of thought and individual creativity. A compendium of selected natural products containing two or more contiguous stereogenic quaternary carbon atoms and key reactions in their total or partial syntheses is provided in the Supporting Information.
authors.affiliation: Department of Chemistry, Université de Montréal, Station Centre-Ville, C. P. 6128, Montréal, Qc, H3C 3J7, Canada.
authors.forename: Martin
authors.initials: M
authors.lastname: Büschleb
authors.affiliation: Department of Chemistry, Université de Montréal, Station Centre-Ville, C. P. 6128, Montréal, Qc, H3C 3J7, Canada.
authors.forename: Stéphane
authors.initials: S
authors.lastname: Dorich
authors.affiliation: Department of Chemistry, Université de Montréal, Station Centre-Ville, C. P. 6128, Montréal, Qc, H3C 3J7, Canada. Stephen.hanessian@umontreal.ca.
authors.forename: Stephen
authors.initials: S
authors.lastname: Hanessian
authors.affiliation: Department of Chemistry, University of California, 1102 Natural Sciences II, Irvine, CA, 92697-2025, USA.
authors.forename: Daniel
authors.initials: D
authors.lastname: Tao
authors.affiliation: Department of Chemistry, University of California, 1102 Natural Sciences II, Irvine, CA, 92697-2025, USA.
authors.forename: Kyle B
authors.initials: KB
authors.lastname: Schenthal
authors.affiliation: Department of Chemistry, University of California, 1102 Natural Sciences II, Irvine, CA, 92697-2025, USA.
authors.forename: Larry E
authors.initials: LE
authors.lastname: Overman
mesh_terms: D001688:Biological Products / Q000138:chemical synthesis* / Q000737:chemistry; D002244:Carbon / Q000032:analysis*
chemical_list: D001688:Biological Products; D002244:Carbon
keywords: biomimetic synthesis; natural products; quaternary carbon atoms; synthetic methods
references.citation: J Org Chem. 2012 Jun 1;77(11):5098-107
references.pmid: 22563879
references.citation: J Nat Prod. 2006 Mar;69(3):418-20
references.pmid: 16562849
references.citation: Angew Chem Int Ed Engl. 2012 May 21;51(21):5217-21
references.pmid: 22499409
references.citation: JAMA. 1998 Nov 11;280(18):1618-9
references.pmid: 9820267
references.citation: Angew Chem Int Ed Engl. 2011 Nov 25;50(48):11501-5
references.pmid: 21990044
references.citation: Org Biomol Chem. 2007 Jan 7;5(1):58-60
references.pmid: 17164906
references.citation: Chemistry. 2009;15(13):3044-55
references.pmid: 19219880
references.citation: Org Lett. 2004 Nov 11;6(23):4327-30
references.pmid: 15524475
references.citation: Org Lett. 2003 Apr 17;5(8):1321-4
references.pmid: 12688749
references.citation: Pharmacogn Rev. 2013 Jan;7(13):47-52
references.pmid: 23922456
references.citation: Nat Prod Rep. 2014 Apr;31(4):550-62
references.pmid: 24595901
references.citation: Nature. 2014 Dec 11;516(7530):181-91
references.pmid: 25503231
references.citation: Angew Chem Int Ed Engl. 2010 Feb 1;49(6):1103-6
references.pmid: 20063336
references.citation: J Am Chem Soc. 2006 Feb 1;128(4):1048-9
references.pmid: 16433500
references.citation: J Org Chem. 1999 Mar 19;64(6):1780-1781
references.pmid: 11674263
references.citation: Chem Rev. 1996 Feb 1;96(1):307-338
references.pmid: 11848755
references.citation: J Am Chem Soc. 2011 Nov 16;133(45):18050-3
references.pmid: 21999462
references.citation: J Am Chem Soc. 2012 Nov 14;134(45):18860-7
references.pmid: 23126440
references.citation: Nat Prod Rep. 2008 Apr;25(2):318-41
references.pmid: 18389140
references.citation: Chem Commun (Camb). 2011 Apr 28;47(16):4593-623
references.pmid: 21359322
references.citation: J Am Chem Soc. 2015 Mar 18;137(10):3510-9
references.pmid: 25756504
references.citation: Life Sci. 2006 Jun 6;79(2):105-11
references.pmid: 16438991
references.citation: J Am Chem Soc. 2014 Dec 24;136(51):17750-6
references.pmid: 25495370
references.citation: Chem Rev. 1996 Feb 1;96(1):339-364
references.pmid: 11848756
references.citation: Agric Biol Chem. 1990 Mar;54(3):657-62
references.pmid: 1368533
references.citation: J Am Chem Soc. 2009 Jul 8;131(26):9168-9
references.pmid: 19522526
references.citation: Angew Chem Int Ed Engl. 1998 Aug 17;37(15):1986-2012
references.pmid: 29711061
references.citation: CNS Drug Rev. 2004 Fall;10(3):203-18
references.pmid: 15492771
references.citation: Angew Chem Int Ed Engl. 2005 Jun 20;44(25):3874-9
references.pmid: 15900527
references.citation: Org Lett. 2002 Oct 31;4(22):3887-90
references.pmid: 12599484
references.citation: J Nat Prod. 2009 Jan;72(1):148-51
references.pmid: 19099464
references.citation: Lancet. 1999 Jun 19;353(9170):2129
references.pmid: 10382704
references.citation: Angew Chem Int Ed Engl. 2001 Dec 17;40(24):4591-4597
references.pmid: 12404360
references.citation: J Am Chem Soc. 2003 Feb 19;125(7):1843-50
references.pmid: 12580611
references.citation: J Org Chem. 2006 Mar 31;71(7):2600-8
references.pmid: 16555810
references.citation: Angew Chem Int Ed Engl. 2009;48(31):5648-52
references.pmid: 19562817
references.citation: J Org Chem. 2005 Mar 4;70(5):1654-70
references.pmid: 15730285
references.citation: J Biol Chem. 1990 Dec 25;265(36):22167-73
references.pmid: 2176205
references.citation: Planta Med. 1998 Aug;64(6):530-5
references.pmid: 9741299
references.citation: Angew Chem Int Ed Engl. 1999;38(8):1134-6
references.pmid: 25138520
references.citation: Org Lett. 2001 May 17;3(10):1475-7
references.pmid: 11388845
references.citation: Chem Rev. 2004 Jul;104(7):3371-404
references.pmid: 15250745
references.citation: Angew Chem Int Ed Engl. 2014 Jun 23;53(26):6701-4
references.pmid: 24838522
references.citation: Angew Chem Int Ed Engl. 2003 Jul 14;42(27):3078-115
references.pmid: 12866094
references.citation: Angew Chem Int Ed Engl. 2000 Jan;39(1):213-215
references.pmid: 10649379
references.citation: Angew Chem Int Ed Engl. 2010 Apr 1;49(15):2750-4
references.pmid: 20229551
references.citation: Mar Drugs. 2010 Jul 08;8(7):2080-116
references.pmid: 20714425
references.citation: Org Lett. 2007 Sep 27;9(20):4033-6
references.pmid: 17760457
references.citation: J Am Chem Soc. 2014 Dec 24;136(51):17738-49
references.pmid: 25409033
references.citation: Antibiotiki. 1971 Jun;16(6):510-3
references.pmid: 5000144
references.citation: Brain Res. 2008 Mar 27;1201:143-50
references.pmid: 18325484
references.citation: Chem Commun (Camb). 2003 Jan 7;(1):68-9
references.pmid: 12610969
references.citation: J Chem Soc Perkin 1. 1968;8:929-36
references.pmid: 5689258
references.citation: Chem Rev. 2001 Dec;101(12):3581-610
references.pmid: 11740916
references.citation: Biosci Biotechnol Biochem. 1999;63(3):515-8
references.pmid: 27393259
references.citation: Angew Chem Int Ed Engl. 2000 Jan;39(1):44-122
references.pmid: 10649349
references.citation: Angew Chem Int Ed Engl. 2013 Dec 2;52(49):12924-7
references.pmid: 24123660
references.citation: J Org Chem. 2009 Dec 4;74(23):9082-93
references.pmid: 19904909
references.citation: Nat Prod Rep. 2009 Jul;26(7):936-62
references.pmid: 19554242
references.citation: Oncogene. 2002 Feb 14;21(8):1242-50
references.pmid: 11850844
references.citation: J Am Chem Soc. 2010 May 26;132(20):7153-76
references.pmid: 20443558
references.citation: J Am Chem Soc. 2010 Dec 1;132(47):16745-6
references.pmid: 21049937
references.citation: Phytochemistry. 2007 Feb;68(4):493-8
references.pmid: 17161442
references.citation: J Am Chem Soc. 2014 Jul 23;136(29):10274-6
references.pmid: 25003871
references.citation: J Org Chem. 2006 Mar 31;71(7):2587-99
references.pmid: 16555809
references.citation: J Am Chem Soc. 2010 May 26;132(20):7138-52
references.pmid: 20443561
references.citation: J Biol Chem. 1998 Feb 6;273(6):3148-51
references.pmid: 9452424
references.citation: J Am Chem Soc. 2015 Aug 26;137(33):10516-9
references.pmid: 26252484
references.citation: Angew Chem Int Ed Engl. 2011 Sep 12;50(38):8863-6
references.pmid: 21638524
references.citation: Angew Chem Int Ed Engl. 2008;47(45):8605-10
references.pmid: 18850598
references.citation: Phytochemistry. 2002 Oct;61(4):439-42
references.pmid: 12377240
references.citation: Angew Chem Int Ed Engl. 2004 Mar 19;43(13):1640-58
references.pmid: 15038029
references.citation: J Am Chem Soc. 2014 Jan 22;136(3):870-3
references.pmid: 24319987
references.citation: J Am Chem Soc. 1988 Jan 1;110(2):649-651
references.pmid: 31527923
references.citation: Org Lett. 2007 Oct 11;9(21):4119-22
references.pmid: 17880227
references.citation: Angew Chem Int Ed Engl. 2007;46(20):3725-8
references.pmid: 17415735
references.citation: European J Org Chem. 2013 May 1;2013(14):2745-2759
references.pmid: 24944521
references.citation: Angew Chem Int Ed Engl. 2013 Mar 25;52(13):3642-5
references.pmid: 23427090
references.citation: J Nat Prod. 1988 Mar-Apr;51(2):345-8
references.pmid: 3379415
references.citation: J Am Chem Soc. 2002 Apr 17;124(15):3808-9
references.pmid: 11942799
references.citation: Nat Prod Rep. 2004 Jun;21(3):321-52
references.pmid: 15162222
references.citation: J Am Chem Soc. 2009 May 20;131(19):6674-5
references.pmid: 19397370
references.citation: Angew Chem Int Ed Engl. 2009;48(39):7140-65
references.pmid: 19714695
references.citation: Tetrahedron Lett. 1987;28(2):175-178
references.pmid: 31595094
references.citation: Tetrahedron Lett. 2009 Nov 25;50(47):6586
references.pmid: 20174449
references.citation: Org Lett. 2004 Nov 11;6(23):4387-90
references.pmid: 15524490
references.citation: Angew Chem Int Ed Engl. 1998 Mar 2;37(4):388-401
references.pmid: 29711174
references.citation: Angew Chem Int Ed Engl. 2007;46(29):5488-508
references.pmid: 17591737
references.citation: Helv Chim Acta. 1971;54(4):1178-90
references.pmid: 5095217
references.citation: Beilstein J Org Chem. 2008;4:31
references.pmid: 18941619
references.citation: Planta Med. 2013 Nov;79(17):1589-98
references.pmid: 24214836
references.citation: Proc Natl Acad Sci U S A. 1996 Dec 10;93(25):14323-7
references.pmid: 8962049
references.citation: J Antibiot (Tokyo). 1979 Feb;32(2):130-5
references.pmid: 571426
references.citation: J Am Chem Soc. 2013 Jan 16;135(2):644-7
references.pmid: 23270309
references.citation: Acc Chem Res. 2007 Feb;40(2):151-61
references.pmid: 17309195
references.citation: J Am Chem Soc. 2006 May 31;128(21):6931-7
references.pmid: 16719473
references.citation: Pharmacol Res. 2002 Dec;46(6):565-8
references.pmid: 12457632
references.citation: J Med Chem. 2002 Oct 10;45(21):4786-93
references.pmid: 12361406
references.citation: Org Lett. 2012 Sep 7;14(17):4354-7
references.pmid: 22891873
references.citation: Biosci Biotechnol Biochem. 1996 Jan;60(3):503-5
references.pmid: 27299554
references.citation: Angew Chem Int Ed Engl. 2009;48(31):5642-7
references.pmid: 19562816
references.citation: Tetrahedron Lett. 1988;29(26):3205-3206
references.pmid: 31595095
references.citation: J Am Chem Soc. 2013 Oct 2;135(39):14552-5
references.pmid: 24047444
references.citation: Proc Natl Acad Sci U S A. 2004 Apr 13;101(15):5363-7
references.pmid: 14724294