title: Catalyst recognition of cis-1,2-diols enables site-selective functionalization of complex molecules.
abstract: Carbohydrates and natural products serve essential roles in nature, and also provide core scaffolds for pharmaceutical agents and vaccines. However, the inherent complexity of these molecules imposes significant synthetic hurdles for their selective functionalization and derivatization. Nature has, in part, addressed these issues by employing enzymes that are able to orient and activate substrates within a chiral pocket, which increases dramatically both the rate and selectivity of organic transformations. In this article we show that similar proximity effects can be utilized in the context of synthetic catalysts to achieve general and predictable site-selective functionalization of complex molecules. Unlike enzymes, our catalysts apply a single reversible covalent bond to recognize and bind to specific functional group displays within substrates. By combining this unique binding selectivity and asymmetric catalysis, we are able to modify the less reactive axial positions within monosaccharides and natural products.
authors: Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
authors: Xixi
authors: X
authors: Sun
authors: Hyelee
authors: H
authors: Lee
authors: Sunggi
authors: S
authors: Lee
authors: Kian L
authors: KL
authors: Tan
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D001688:Biological Products / Q000737:chemistry; D002384:Catalysis; D007536:Isomerism; D009005:Monosaccharides / Q000737:chemistry
chemical_list: D000438:Alcohols; D001688:Biological Products; D009005:Monosaccharides
references: Acc Chem Res. 2012 Jun 19;45(6):826-39
references: 22017496
references: J Am Chem Soc. 1977 Feb 2;99(3):905-115
references: 833385
references: Nature. 2011 Jun 22;474(7352):461-6
references: 21697944
references: J Am Chem Soc. 2011 Mar 23;133(11):3724-7
references: 21355584
references: Nat Immunol. 2008 Jun;9(6):593-601
references: 18490910
references: Angew Chem Int Ed Engl. 2006 Aug 25;45(34):5616-9
references: 16858713
references: J Am Chem Soc. 2012 May 16;134(19):8260-7
references: 22533533
references: Chem Soc Rev. 2008 Dec;37(12):2668-75
references: 19020680
references: Science. 2007 Nov 2;318(5851):783-7
references: 17975062
references: J Am Chem Soc. 2013 Jun 5;135(22):8415-22
references: 23692563
references: J Am Chem Soc. 2012 May 2;134(17):7321-4
references: 22515351
references: Proc Natl Acad Sci U S A. 1971 Aug;68(8):1678-83
references: 5288752
references: J Am Chem Soc. 2012 Oct 10;134(40):16571-7
references: 22971001
references: J Am Chem Soc. 1973 May 16;95(10):3251-62
references: 4708826
references: J Am Chem Soc. 2007 Oct 24;129(42):12890-5
references: 17902666
references: J Biol Chem. 2004 Apr 23;279(17):17921-31
references: 14752117
references: Nat Rev Microbiol. 2010 Apr;8(4):281-9
references: 20190824
references: J Org Chem. 2009 Nov 20;74(22):8802-5
references: 19908913
references: J Am Chem Soc. 2012 Apr 11;134(14):6120-3
references: 22462775
references: Org Lett. 2011 Aug 5;13(15):3794-7
references: 21714486
references: Angew Chem Int Ed Engl. 2007;46(44):8471-4
references: 17899619
references: Org Lett. 2011 Aug 5;13(15):3778-81
references: 21711005
references: Angew Chem Int Ed Engl. 2012 Oct 29;51(44):10954-90
references: 23011639
references: Org Lett. 2011 Jun 17;13(12):3090-3
references: 21591630
references: J Am Chem Soc. 2012 Oct 3;134(39):16430-3
references: 22954207
references: Angew Chem Int Ed Engl. 2011 Dec 9;50(50):11872-923
references: 22127846
references: Org Lett. 2013 Mar 15;15(6):1358-61
references: 23465047
references: Chemistry. 2013 Feb 18;19(8):2597-601
references: 23307591
references: Org Biomol Chem. 2010 Apr 7;8(7):1497-504
references: 20237658
references: Nat Rev Drug Discov. 2005 Sep;4(9):751-63
references: 16138107
references: Nat Prod Rep. 1997 Apr;14(2):99-110
references: 9149408
references: Science. 2001 Mar 23;291(5512):2364-9
references: 11269317
references: Nat Chem. 2012 Dec;4(12):996-1003
references: 23174979
references: Nature. 2006 Sep 7;443(7107):67-70
references: 16957727
references: Angew Chem Int Ed Engl. 2009;48(11):1900-34
references: 19173361
references: Nat Prod Rep. 2008 Jun;25(3):475-516
references: 18497896
references: J Am Chem Soc. 2012 Jun 13;134(23):9755-61
references: 22621706
references: Science. 1999 Aug 13;285(5430):1074-7
references: 10446055
references: J Am Chem Soc. 2011 Sep 7;133(35):13926-9
references: 21838223
references: Angew Chem Int Ed Engl. 2011 Aug 22;50(35):8167-71
references: 21739552
references: Top Curr Chem. 2016;372:125-55
references: 26287121
references: Nat Prod Rep. 2011 Mar;28(3):630-48
references: 21120227