Does Neighboring Group Participation by Non-vicinal Esters Play a Role in Glycosylation Reactions? Effective Probes for the Detection of Bridging Intermediates

Overview

Journal J Org Chem

Publisher American Chemical Society

Specialty Chemistry

Date 2008 Oct 23

PMID 18939876

Citations 35

Authors

David Crich

Tianshun Hu

Feng Cai

Affiliations

Soon will be listed here.

Abstract

Neighboring group participation in glycopyranosylation reactions is probed for esters at the 3-O-axial and -equatorial, 4-O-axial and -equatorial, and 6-O-sites of a range of donors through the use tert-butoxycarbonyl esters. The anticipated intermediate cyclic dioxanyl cation is interrupted for the axial 3-O-derivative, leading to the formation of a 1,3-O-cyclic carbonate ester, with loss of a tert-butyl cation, providing convincing evidence of participation by esters at that position. However, no evidence was found for such a fragmentation of carbonate esters at the 3-O-equatorial, 4-O-axial and -equatorial, and 6-O positions, indicating that neighboring group participation from those sites does not occur under typical glycosylation conditions. Further probes employing a 4-O-(2-carboxy)benzoate ester and a 4-O-(4-methoxybenzoate) ester, the latter in conjunction with an (18)O quench designed to detect bridging intermediates, also failed to provide evidence for participation by 4-O-esters in galactopyranosylation.

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References

Crich D, Vinogradova O . On the influence of the C2-O2 and C3-O3 bonds in 4,6-O-benzylidene-directed beta-mannopyranosylation and alpha-glucopyranosylation. J Org Chem. 2006; 71(22):8473-80. PMC: 2621314. DOI: 10.1021/jo061417b. View

Crich D, Wu B . 1-naphthylpropargyl ether group: a readily cleaved and sterically minimal protecting system for stereoselective glycosylation. Org Lett. 2006; 8(21):4879-82. PMC: 2615467. DOI: 10.1021/ol061938l. View

Tanaka H, Yoshizawa A, Takahashi T . Direct and stereoselective synthesis of beta-linked 2,6-deoxyoligosaccharides. Angew Chem Int Ed Engl. 2007; 46(14):2505-7. DOI: 10.1002/anie.200604031. View

Crich D, Li M . Revisiting the armed-disarmed concept: the importance of anomeric configuration in the activation of S-benzoxazolyl glycosides. Org Lett. 2007; 9(21):4115-8. PMC: 3221596. DOI: 10.1021/ol701466u. View

Jiao H, Hindsgaul O . The 2-N,N-Dibenzylamino Group as a Participating Group in the Synthesis of β-Glycosides. Angew Chem Int Ed Engl. 2018; 38(3):346-348. DOI: 10.1002/(SICI)1521-3773(19990201)38:3<346::AID-ANIE346>3.0.CO;2-L. View

Beaver M, Billings S, Woerpel K . C-glycosylation reactions of sulfur-substituted glycosyl donors: evidence against the role of neighboring-group participation. J Am Chem Soc. 2008; 130(6):2082-6. DOI: 10.1021/ja0767783. View

Kulkarni S, Liu Y, Hung S . Neighboring group participation of 9-anthracenylmethyl group in glycosylation: preparation of unusual C-glycosides. J Org Chem. 2005; 70(7):2808-11. DOI: 10.1021/jo047794a. View

Fan E, Shi W, Lowary T . Synthesis of daunorubicin analogues containing truncated aromatic cores and unnatural monosaccharide residues. J Org Chem. 2007; 72(8):2917-28. DOI: 10.1021/jo062542q. View

El-Badri M, Willenbring D, Tantillo D, Gervay-Hague J . Mechanistic studies on the stereoselective formation of beta-mannosides from mannosyl iodides using alpha-deuterium kinetic isotope effects. J Org Chem. 2007; 72(13):4663-72. DOI: 10.1021/jo070229y. View

10.

Jensen H, Pedersen C, Bols M . Going to extremes: "super" armed glycosyl donors in glycosylation chemistry. Chemistry. 2007; 13(27):7576-82. DOI: 10.1002/chem.200700947. View

11.

Crich D, Yao Q . Benzylidene acetal fragmentation route to 6-deoxy sugars: direct reductive cleavage in the presence of ether protecting groups, permitting the efficient, highly stereocontrolled synthesis of beta-D-rhamnosides from D-mannosyl glycosyl donors. Total.... J Am Chem Soc. 2004; 126(26):8232-6. DOI: 10.1021/ja048070j. View

12.

Jensen H, Bols M . Stereoelectronic substituent effects. Acc Chem Res. 2006; 39(4):259-65. DOI: 10.1021/ar050189p. View

13.

Grayson E, Ward S, Hall A, Rendle P, Gamblin D, Batsanov A . Glycosyl disulfides: novel glycosylating reagents with flexible aglycon alteration. J Org Chem. 2005; 70(24):9740-54. DOI: 10.1021/jo051374j. View

14.

Okada Y, Nagata O, Taira M, Yamada H . Highly beta-selective and direct formation of 2-O-glycosylated glucosides by ring restriction into twist-boat. Org Lett. 2007; 9(15):2755-8. DOI: 10.1021/ol070720b. View

15.

Kim J, Yang H, Park J, Boons G . A general strategy for stereoselective glycosylations. J Am Chem Soc. 2005; 127(34):12090-7. DOI: 10.1021/ja052548h. View

16.

McDonnell C, Lopez O, Murphy P, Fernandez Bolanos J, Hazell R, Bols M . Conformational effects on glycoside reactivity: study of the high reactive conformer of glucose. J Am Chem Soc. 2004; 126(39):12374-85. DOI: 10.1021/ja047476t. View

17.

Crich D, Jayalath P, Hutton T . Enhanced diastereoselectivity in beta-mannopyranosylation through the use of sterically minimal propargyl ether protecting groups. J Org Chem. 2006; 71(8):3064-70. PMC: 4664462. DOI: 10.1021/jo0526789. View

18.

Gunther W, Kunz H . Synthesis of beta-D-mannosides from beta-D-glucosides via an intramolecular SN2 reaction at C-2. Carbohydr Res. 1992; 228(1):217-41. DOI: 10.1016/s0008-6215(00)90561-5. View

19.

Crich D, Vinod A, Picione J . The 3,4-O-carbonate protecting group as a beta-directing group in rhamnopyranosylation in both homogeneous and heterogeneous glycosylations as compared to the chameleon-like 2,3-O-carbonates. J Org Chem. 2003; 68(22):8453-8. DOI: 10.1021/jo035003j. View

20.

Crich D, Cai W, Dai Z . Highly diastereoselective alpha-mannopyranosylation in the absence of participating protecting groups. J Org Chem. 2000; 65(5):1291-7. DOI: 10.1021/jo9910482. View