Diastereoselective Synthesis of Aryl C-Glycosides from Glycosyl Esters Via C-O Bond Homolysis

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2021 Jan 13

PMID 33438338

Citations 23

Authors

Yongliang Wei

Benjamin Ben-Zvi

Tianning Diao

Affiliations

Soon will be listed here.

Abstract

C-aryl glycosyl compounds offer better in vivo stability relative to O- and N-glycoside analogues. C-aryl glycosides are extensively investigated as drug candidates and applied to chemical biology studies. Previously, C-aryl glycosides were derived from lactones, glycals, glycosyl stannanes, and halides, via methods displaying various limitations with respect to the scope, functional-group compatibility, and practicality. Challenges remain in the synthesis of C-aryl nucleosides and 2-deoxysugars from easily accessible carbohydrate precursors. Herein, we report a cross-coupling method to prepare C-aryl and heteroaryl glycosides, including nucleosides and 2-deoxysugars, from glycosyl esters and bromoarenes. Activation of the carbohydrate substrates leverages dihydropyridine (DHP) as an activating group followed by decarboxylation to generate a glycosyl radical via C-O bond homolysis. This strategy represents a new means to activate alcohols as a cross-coupling partner. The convenient preparation of glycosyl esters and their stability exemplifies the potential of this method in medicinal chemistry.

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References

Popsavin M, Torovic L, Svircev M, Kojic V, Bogdanovic G, Popsavin V . Synthesis and antiproliferative activity of two new tiazofurin analogues with 2'-amido functionalities. Bioorg Med Chem Lett. 2006; 16(10):2773-6. DOI: 10.1016/j.bmcl.2006.02.001. View

Alandini N, Buzzetti L, Favi G, Schulte T, Candish L, Collins K . Amide Synthesis by Nickel/Photoredox-Catalyzed Direct Carbamoylation of (Hetero)Aryl Bromides. Angew Chem Int Ed Engl. 2020; 59(13):5248-5253. PMC: 7155093. DOI: 10.1002/anie.202000224. View

Adero P, Amarasekara H, Wen P, Bohe L, Crich D . The Experimental Evidence in Support of Glycosylation Mechanisms at the S1-S2 Interface. Chem Rev. 2018; 118(17):8242-8284. PMC: 6135681. DOI: 10.1021/acs.chemrev.8b00083. View

Stache E, Ertel A, Tomislav R, Doyle A . Generation of Phosphoranyl Radicals via Photoredox Catalysis Enables Voltage-Independent Activation of Strong C-O Bonds. ACS Catal. 2019; 8(12):11134-11139. PMC: 6668916. DOI: 10.1021/acscatal.8b03592. View

Wellington K, Benner S . A review: synthesis of aryl C-glycosides via the heck coupling reaction. Nucleosides Nucleotides Nucleic Acids. 2006; 25(12):1309-33. DOI: 10.1080/15257770600917013. View

Nawrat C, Jamison C, Slutskyy Y, MacMillan D, Overman L . Oxalates as Activating Groups for Alcohols in Visible Light Photoredox Catalysis: Formation of Quaternary Centers by Redox-Neutral Fragment Coupling. J Am Chem Soc. 2015; 137(35):11270-11273. PMC: 4632490. DOI: 10.1021/jacs.5b07678. View

Guo J, Wang S, Dai N, Teo Y, Kool E . Multispectral labeling of antibodies with polyfluorophores on a DNA backbone and application in cellular imaging. Proc Natl Acad Sci U S A. 2011; 108(9):3493-8. PMC: 3048162. DOI: 10.1073/pnas.1017349108. View

Zhang X, MacMillan D . Alcohols as Latent Coupling Fragments for Metallaphotoredox Catalysis: sp-sp Cross-Coupling of Oxalates with Aryl Halides. J Am Chem Soc. 2016; 138(42):13862-13865. PMC: 5464990. DOI: 10.1021/jacs.6b09533. View

Lackner G, Quasdorf K, Overman L . Direct construction of quaternary carbons from tertiary alcohols via photoredox-catalyzed fragmentation of tert-alkyl N-phthalimidoyl oxalates. J Am Chem Soc. 2013; 135(41):15342-5. PMC: 3856227. DOI: 10.1021/ja408971t. View

10.

Shi Z, Sun L, Li C . Solvent Polarity-Controlled Selective Synthesis of Methyl Pyranoside and Furanoside. J Agric Food Chem. 2014; 62(14):3287-3292. DOI: 10.1021/jf500144b. View

11.

Gong H, Gagne M . Diastereoselective Ni-catalyzed Negishi cross-coupling approach to saturated, fully oxygenated C-alkyl and C-aryl glycosides. J Am Chem Soc. 2008; 130(36):12177-83. DOI: 10.1021/ja8041564. View

12.

Gutierrez-Bonet A, Tellis J, Matsui J, Vara B, Molander G . 1,4-Dihydropyridines as Alkyl Radical Precursors: Introducing the Aldehyde Feedstock to Nickel/Photoredox Dual Catalysis. ACS Catal. 2016; 6(12):8004-8008. PMC: 5152669. DOI: 10.1021/acscatal.6b02786. View

13.

Lv W, Chen Y, Wen S, Ba D, Cheng G . Modular and Stereoselective Synthesis of C-Aryl Glycosides via Catellani Reaction. J Am Chem Soc. 2020; 142(35):14864-14870. DOI: 10.1021/jacs.0c07634. View

14.

Ghosh T, Mukherji A, Srivastava H, Kancharla P . Secondary amine salt catalyzed controlled activation of 2-deoxy sugar lactols towards alpha-selective dehydrative glycosylation. Org Biomol Chem. 2018; 16(16):2870-2875. DOI: 10.1039/c8ob00423d. View

15.

Stambasky J, Hocek M, Kocovsky P . C-nucleosides: synthetic strategies and biological applications. Chem Rev. 2009; 109(12):6729-64. DOI: 10.1021/cr9002165. View

16.

De Clercq E . C-Nucleosides To Be Revisited. J Med Chem. 2015; 59(6):2301-11. DOI: 10.1021/acs.jmedchem.5b01157. View

17.

Matulic-Adamic J, Beigelman L, Portmann S, Egli M, Usman N . Synthesis and Structure of 1-Deoxy-1-phenyl-beta-D-ribofuranose and Its Incorporation into Oligonucleotides. J Org Chem. 1996; 61(11):3909-3911. DOI: 10.1021/jo960091b. View

18.

Anderson J, Daifuku R, Loeb L . Viral error catastrophe by mutagenic nucleosides. Annu Rev Microbiol. 2004; 58:183-205. DOI: 10.1146/annurev.micro.58.030603.123649. View

19.

Shen Y, Gu Y, Martin R . sp C-H Arylation and Alkylation Enabled by the Synergy of Triplet Excited Ketones and Nickel Catalysts. J Am Chem Soc. 2018; 140(38):12200-12209. DOI: 10.1021/jacs.8b07405. View

20.

Brotschi C, Mathis G, Leumann C . Bipyridyl- and biphenyl-DNA: a recognition motif based on interstrand aromatic stacking. Chemistry. 2005; 11(6):1911-23. DOI: 10.1002/chem.200400858. View