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Stereodirecting Effect of C5-Carboxylate Substituents on the Glycosylation Stereochemistry of 3-Deoxy-d- manno-oct-2-ulosonic Acid (Kdo) Thioglycoside Donors: Stereoselective Synthesis of α- and β-Kdo Glycosides.
J Am Chem Soc. 2018 03 14; 140(10):3574-3582.JA

Abstract

The stereodirecting effect of C5-ester functions on the glycosylation stereoselectivity of 3-deoxy-d- manno-oct-2-ulosonic acid (Kdo) ethyl thioglycoside donors is presented. The coupling of 5- O-arylcarbonyl or acetyl protected Kdo thioglycosides with acceptors proceeds in an α-selective and high-yielding manner, leading to formation of α-linked Kdo glycosides products. On the other hand, the glycosylation stereoselectivity of the 5- O-2-quinolinecarbonyl (Quin) or 4-nitropicoloyl substituted Kdo thioglycoside donors is switchable: (1) The glycosylation of the 5- O-Quin carrying Kdo donors with primary glycosyl acceptors shows complete β-stereoselectivity, furnishing the corresponding β-glycosides in good-to-excellent yield. (2) The stereochemical outcome of the secondary acceptors with these Kdo donors is determined mainly by the stereoelectronic nature of the acceptor. Only or predominant α anomeric products are obtained when the Kdo donors couple with the disarmed or highly crowded secondary carbohydrate acceptors, while the selectivity may switch to predominant β in the glycosylation of the 5- O-4-nitropicoloyl carrying donor with more reactive secondary alcohols. The synthetic use of the newly developed Kdo donors 1c and 7b has been demonstrated by facile preparation of a structurally unique trisaccharide motif 19 which possesses both α- and β-Kdo glycosidic bonds.

Authors+Show Affiliations

Department of Chemistry of Medicinal Natural Products, Sichuan Engineering Laboratory for Plant-Sourced Drug and Research Center for Drug Industrial Technology, West China School of Pharmacy, and State Key Laboratory of Biotherapy , West China Hospital, Sichuan University , Chengdu 610041 , China.Department of Chemistry of Medicinal Natural Products, Sichuan Engineering Laboratory for Plant-Sourced Drug and Research Center for Drug Industrial Technology, West China School of Pharmacy, and State Key Laboratory of Biotherapy , West China Hospital, Sichuan University , Chengdu 610041 , China.Department of Chemistry of Medicinal Natural Products, Sichuan Engineering Laboratory for Plant-Sourced Drug and Research Center for Drug Industrial Technology, West China School of Pharmacy, and State Key Laboratory of Biotherapy , West China Hospital, Sichuan University , Chengdu 610041 , China.Department of Chemistry of Medicinal Natural Products, Sichuan Engineering Laboratory for Plant-Sourced Drug and Research Center for Drug Industrial Technology, West China School of Pharmacy, and State Key Laboratory of Biotherapy , West China Hospital, Sichuan University , Chengdu 610041 , China.Department of Chemistry of Medicinal Natural Products, Sichuan Engineering Laboratory for Plant-Sourced Drug and Research Center for Drug Industrial Technology, West China School of Pharmacy, and State Key Laboratory of Biotherapy , West China Hospital, Sichuan University , Chengdu 610041 , China.Department of Chemistry of Medicinal Natural Products, Sichuan Engineering Laboratory for Plant-Sourced Drug and Research Center for Drug Industrial Technology, West China School of Pharmacy, and State Key Laboratory of Biotherapy , West China Hospital, Sichuan University , Chengdu 610041 , China.Department of Chemistry of Medicinal Natural Products, Sichuan Engineering Laboratory for Plant-Sourced Drug and Research Center for Drug Industrial Technology, West China School of Pharmacy, and State Key Laboratory of Biotherapy , West China Hospital, Sichuan University , Chengdu 610041 , China.Department of Chemistry of Medicinal Natural Products, Sichuan Engineering Laboratory for Plant-Sourced Drug and Research Center for Drug Industrial Technology, West China School of Pharmacy, and State Key Laboratory of Biotherapy , West China Hospital, Sichuan University , Chengdu 610041 , China.

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

29481074

Citation

Huang, Wei, et al. "Stereodirecting Effect of C5-Carboxylate Substituents On the Glycosylation Stereochemistry of 3-Deoxy-d- Manno-oct-2-ulosonic Acid (Kdo) Thioglycoside Donors: Stereoselective Synthesis of Α- and β-Kdo Glycosides." Journal of the American Chemical Society, vol. 140, no. 10, 2018, pp. 3574-3582.
Huang W, Zhou YY, Pan XL, et al. Stereodirecting Effect of C5-Carboxylate Substituents on the Glycosylation Stereochemistry of 3-Deoxy-d- manno-oct-2-ulosonic Acid (Kdo) Thioglycoside Donors: Stereoselective Synthesis of α- and β-Kdo Glycosides. J Am Chem Soc. 2018;140(10):3574-3582.
Huang, W., Zhou, Y. Y., Pan, X. L., Zhou, X. Y., Lei, J. C., Liu, D. M., Chu, Y., & Yang, J. S. (2018). Stereodirecting Effect of C5-Carboxylate Substituents on the Glycosylation Stereochemistry of 3-Deoxy-d- manno-oct-2-ulosonic Acid (Kdo) Thioglycoside Donors: Stereoselective Synthesis of α- and β-Kdo Glycosides. Journal of the American Chemical Society, 140(10), 3574-3582. https://doi.org/10.1021/jacs.7b09461
Huang W, et al. Stereodirecting Effect of C5-Carboxylate Substituents On the Glycosylation Stereochemistry of 3-Deoxy-d- Manno-oct-2-ulosonic Acid (Kdo) Thioglycoside Donors: Stereoselective Synthesis of Α- and β-Kdo Glycosides. J Am Chem Soc. 2018 03 14;140(10):3574-3582. PubMed PMID: 29481074.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Stereodirecting Effect of C5-Carboxylate Substituents on the Glycosylation Stereochemistry of 3-Deoxy-d- manno-oct-2-ulosonic Acid (Kdo) Thioglycoside Donors: Stereoselective Synthesis of α- and β-Kdo Glycosides. AU - Huang,Wei, AU - Zhou,Ying-Yu, AU - Pan,Xing-Ling, AU - Zhou,Xian-Yang, AU - Lei,Jin-Cai, AU - Liu,Dong-Mei, AU - Chu,Yue, AU - Yang,Jin-Song, Y1 - 2018/03/06/ PY - 2018/2/27/pubmed PY - 2018/6/26/medline PY - 2018/2/27/entrez SP - 3574 EP - 3582 JF - Journal of the American Chemical Society JO - J. Am. Chem. Soc. VL - 140 IS - 10 N2 - The stereodirecting effect of C5-ester functions on the glycosylation stereoselectivity of 3-deoxy-d- manno-oct-2-ulosonic acid (Kdo) ethyl thioglycoside donors is presented. The coupling of 5- O-arylcarbonyl or acetyl protected Kdo thioglycosides with acceptors proceeds in an α-selective and high-yielding manner, leading to formation of α-linked Kdo glycosides products. On the other hand, the glycosylation stereoselectivity of the 5- O-2-quinolinecarbonyl (Quin) or 4-nitropicoloyl substituted Kdo thioglycoside donors is switchable: (1) The glycosylation of the 5- O-Quin carrying Kdo donors with primary glycosyl acceptors shows complete β-stereoselectivity, furnishing the corresponding β-glycosides in good-to-excellent yield. (2) The stereochemical outcome of the secondary acceptors with these Kdo donors is determined mainly by the stereoelectronic nature of the acceptor. Only or predominant α anomeric products are obtained when the Kdo donors couple with the disarmed or highly crowded secondary carbohydrate acceptors, while the selectivity may switch to predominant β in the glycosylation of the 5- O-4-nitropicoloyl carrying donor with more reactive secondary alcohols. The synthetic use of the newly developed Kdo donors 1c and 7b has been demonstrated by facile preparation of a structurally unique trisaccharide motif 19 which possesses both α- and β-Kdo glycosidic bonds. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/29481074/Stereodirecting_Effect_of_C5_Carboxylate_Substituents_on_the_Glycosylation_Stereochemistry_of_3_Deoxy_d__manno_oct_2_ulosonic_Acid__Kdo__Thioglycoside_Donors:_Stereoselective_Synthesis_of_α__and_β_Kdo_Glycosides_ L2 - https://dx.doi.org/10.1021/jacs.7b09461 DB - PRIME DP - Unbound Medicine ER -