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糖基卤化物的合成与糖苷化:从 20 世纪早期研究到现代方法的发展历程。

Synthesis and Glycosidation of Anomeric Halides: Evolution from Early Studies to Modern Methods of the 21st Century.

机构信息

Department of Chemistry and Biochemistry, University of Missouri-St. Louis, One University Boulevard, St. Louis, Missouri 63121, United States.

Department of Chemistry, Saint Louis University, 3501 Laclede Avenue, St. Louis, Missouri 63103, United States.

出版信息

Chem Rev. 2022 Jul 13;122(13):11701-11758. doi: 10.1021/acs.chemrev.2c00029. Epub 2022 Jun 8.

DOI:10.1021/acs.chemrev.2c00029
PMID:35675037
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9417321/
Abstract

Advances in synthetic carbohydrate chemistry have dramatically improved access to common glycans. However, many novel methods still fail to adequately address challenges associated with chemical glycosylation and glycan synthesis. Since a challenge of glycosylation has remained, scientists have been frequently returning to the traditional glycosyl donors. This review is dedicated to glycosyl halides that have played crucial roles in shaping the field of glycosciences and continue to pave the way toward our understanding of chemical glycosylation.

摘要

合成碳水化合物化学的进步极大地改善了常见糖的获取途径。然而,许多新方法仍然无法充分解决与化学糖基化和聚糖合成相关的挑战。由于糖基化的挑战仍然存在,科学家们经常回到传统的糖基供体。本综述专门介绍了卤代糖基,它们在塑造糖科学领域方面发挥了关键作用,并为我们对化学糖基化的理解铺平了道路。

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1
Synthesis and Glycosidation of Anomeric Halides: Evolution from Early Studies to Modern Methods of the 21st Century.糖基卤化物的合成与糖苷化:从 20 世纪早期研究到现代方法的发展历程。
Chem Rev. 2022 Jul 13;122(13):11701-11758. doi: 10.1021/acs.chemrev.2c00029. Epub 2022 Jun 8.
2
Venturing beyond Donor-Controlled Glycosylation: New Perspectives toward Anomeric Selectivity.超越供体控制的糖基化:对端基选择性的新视角。
Acc Chem Res. 2018 Mar 20;51(3):628-639. doi: 10.1021/acs.accounts.7b00449. Epub 2018 Feb 22.
3
Donor Preactivation-Based Glycan Assembly: from Manual to Automated Synthesis.基于供体预活化的聚糖组装:从手动合成到自动合成
Acc Chem Res. 2024 Jun 4;57(11):1577-1594. doi: 10.1021/acs.accounts.4c00072. Epub 2024 Apr 15.
4
En Route to the Transformation of Glycoscience: A Chemist's Perspective on Internal and External Crossroads in Glycochemistry.在糖科学转型的路上:糖化学内部和外部十字路口的化学家视角。
J Am Chem Soc. 2021 Jan 13;143(1):17-34. doi: 10.1021/jacs.0c11106. Epub 2020 Dec 22.
5
Taming the Reactivity of Glycosyl Iodides To Achieve Stereoselective Glycosidation.糖苷碘化试剂的反应性控制实现立体选择性糖苷化。
Acc Chem Res. 2016 Jan 19;49(1):35-47. doi: 10.1021/acs.accounts.5b00357. Epub 2015 Nov 2.
6
Iodine-triphenylphosphine triggers an easy one-pot alpha stereoselective dehydrative glycosylation on hemiacetalic benzylated glycosyl donors.碘三苯膦引发了在半缩醛苄基化糖基给体上易于一锅法 α 立体选择性脱水糖基化的反应。
Carbohydr Res. 2023 Nov;533:108944. doi: 10.1016/j.carres.2023.108944. Epub 2023 Sep 16.
7
Glycosyl Cross-Coupling of Anomeric Nucleophiles: Scope, Mechanism, and Applications in the Synthesis of Aryl C-Glycosides.糖基交叉偶联反应:反应范围、反应机理及其在芳基 C-糖苷合成中的应用。
J Am Chem Soc. 2017 Dec 13;139(49):17908-17922. doi: 10.1021/jacs.7b08707. Epub 2017 Nov 30.
8
Synthesis of N-glycan oxazolines: donors for endohexosaminidase catalysed glycosylation.N-聚糖恶唑啉的合成:用于内切己糖胺酶催化糖基化的供体
Carbohydr Res. 2006 Jul 24;341(10):1574-96. doi: 10.1016/j.carres.2006.03.007. Epub 2006 Apr 11.
9
Stable Alkynyl Glycosyl Carbonates: Catalytic Anomeric Activation and Synthesis of a Tridecasaccharide Reminiscent of Mycobacterium tuberculosis Cell Wall Lipoarabinomannan.稳定的炔基糖基碳酸酯:催化的端基异构激活和十三糖的合成,类似于结核分枝杆菌细胞壁脂阿拉伯甘露聚糖。
Angew Chem Int Ed Engl. 2016 Jun 27;55(27):7786-91. doi: 10.1002/anie.201511695. Epub 2016 Feb 16.
10
A minimalist approach to stereoselective glycosylation with unprotected donors.一种非保护基供体的立体选择性糖基化的极简方法。
Nat Commun. 2017 Oct 27;8(1):1146. doi: 10.1038/s41467-017-01073-7.

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Floridoside Phosphotriester Derivatives: Synthesis and Inhibition of Human Neutrophils' Oxidative Burst.佛罗里多苷磷酸三酯衍生物:合成及对人中性粒细胞氧化爆发的抑制作用
Molecules. 2025 Jul 3;30(13):2850. doi: 10.3390/molecules30132850.
2
Phenanthroline-Assisted Stereoselective Synthesis of 2-Deoxy Glycosides.菲咯啉辅助的2-脱氧糖苷的立体选择性合成
ACS Omega. 2025 Apr 29;10(18):18700-18708. doi: 10.1021/acsomega.5c00189. eCollection 2025 May 13.
3
Immunological and Toxicological Assessment of Triterpenoid Saponins Bearing Lewis-X- and QS-21-Based Trisaccharides.

本文引用的文献

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Electrochemical Synthesis of Glycosyl Fluorides Using Sulfur(VI) Hexafluoride as the Fluorinating Agent.使用六氟化硫作为氟化剂电化学合成糖基氟化物。
Org Lett. 2022 Apr 1;24(12):2294-2298. doi: 10.1021/acs.orglett.2c00431. Epub 2022 Mar 17.
2
Revisiting Glycosylations Using Glycosyl Fluoride by BF·EtO: Activation of Disarmed Glycosyl Fluorides with High Catalytic Turnover.使用 BF·EtO 重访糖苷化:具有高催化周转率的去武装糖苷化试剂的激活。
Org Lett. 2022 Jan 14;24(1):6-10. doi: 10.1021/acs.orglett.1c03233. Epub 2021 Dec 21.
3
Guidelines for -Glycoside Formation from First Principles.
携带基于Lewis-X和QS-21的三糖的三萜皂苷的免疫学和毒理学评估。
Chemistry. 2025 May 19;31(28):e202500994. doi: 10.1002/chem.202500994. Epub 2025 Apr 21.
4
Synthesis of 2-Deoxyglycosides with Exclusive β-Configuration Using 2-SAc Glycosyl Bromide Donors.使用2-SAc糖基溴供体合成具有单一β-构型的2-脱氧糖苷。
Molecules. 2025 Jan 5;30(1):185. doi: 10.3390/molecules30010185.
5
Stereoselective chemical N-glycoconjugation of amines via CO incorporation.通过一氧化碳插入实现胺的立体选择性化学N-糖缀合。
Nat Commun. 2024 Nov 29;15(1):10373. doi: 10.1038/s41467-024-54523-4.
6
Development of ketalized unsaturated saccharides as multifunctional cysteine-targeting covalent warheads.酮缩醛化不饱和糖作为多功能靶向半胱氨酸的共价弹头的开发。
Commun Chem. 2024 Sep 9;7(1):201. doi: 10.1038/s42004-024-01279-z.
7
Electrochemical Glycosylation via Halogen-Atom-Transfer for -Glycoside Assembly.通过卤原子转移实现电化学糖基化用于糖苷组装
ACS Catal. 2024 Jul 19;14(15):11532-11544. doi: 10.1021/acscatal.4c02322. eCollection 2024 Aug 2.
8
Catalytic glycosylation for minimally protected donors and acceptors.催化糖基化用于最小保护供体和受体。
Nature. 2024 Aug;632(8024):313-319. doi: 10.1038/s41586-024-07695-4. Epub 2024 Jun 17.
9
SFox imidates as versatile glycosyl donors for chemical glycosylation.S-氟代亚胺作为化学糖基化中通用的糖基供体。
Org Biomol Chem. 2024 Jun 26;22(25):5214-5223. doi: 10.1039/d4ob00679h.
10
Direct Synthesis of Glycosyl Chlorides from Thioglycosides.直接从硫代糖苷合成糖苷氯化物。
J Org Chem. 2024 May 17;89(10):6865-6876. doi: 10.1021/acs.joc.4c00244. Epub 2024 Apr 26.
基于第一性原理的糖苷形成指南。
ACS Cent Sci. 2021 Sep 22;7(9):1454-1462. doi: 10.1021/acscentsci.1c00594. Epub 2021 Aug 13.
4
Automated, Multistep Continuous-Flow Synthesis of 2,6-Dideoxy and 3-Amino-2,3,6-trideoxy Monosaccharide Building Blocks.自动化、多步骤连续流合成 2,6-二脱氧和 3-氨基-2,3,6-三脱氧单糖砌块。
Angew Chem Int Ed Engl. 2021 Oct 18;60(43):23171-23175. doi: 10.1002/anie.202109887. Epub 2021 Sep 21.
5
Diastereoselective sp C-O Bond Formation via Visible Light-Induced, Copper-Catalyzed Cross-Couplings of Glycosyl Bromides with Aliphatic Alcohols.通过可见光诱导、铜催化的糖基溴化物与脂肪醇的交叉偶联实现非对映选择性sp C-O键的形成。
ACS Catal. 2020 Jun 5;10(11):5990-6001. doi: 10.1021/acscatal.0c01470. Epub 2020 Apr 29.
6
Bismuth(iii) triflate as a novel and efficient activator for glycosyl halides.三氟甲磺酸铋作为一种新型高效的糖基卤化物活化剂。
Org Biomol Chem. 2021 Apr 14;19(14):3220-3233. doi: 10.1039/d1ob00093d. Epub 2021 Mar 24.
7
Discovery of Semi- and Fully-Synthetic Carbohydrate Vaccines Against Bacterial Infections Using a Medicinal Chemistry Approach.采用药物化学方法发现针对细菌性感染的半合成和全合成碳水化合物疫苗。
Chem Rev. 2021 Apr 14;121(7):3598-3626. doi: 10.1021/acs.chemrev.0c01210. Epub 2021 Apr 1.
8
Synthesis of Glycosyl Fluorides by Photochemical Fluorination with Sulfur(VI) Hexafluoride.六氟化硫的光氟化法合成糖基氟化物。
Org Lett. 2021 Jan 1;23(1):190-194. doi: 10.1021/acs.orglett.0c03915. Epub 2020 Dec 23.
9
En Route to the Transformation of Glycoscience: A Chemist's Perspective on Internal and External Crossroads in Glycochemistry.在糖科学转型的路上:糖化学内部和外部十字路口的化学家视角。
J Am Chem Soc. 2021 Jan 13;143(1):17-34. doi: 10.1021/jacs.0c11106. Epub 2020 Dec 22.
10
Stereocontrolled α-Galactosylation under Cooperative Catalysis.协同催化下的立体控制α-半乳糖基化反应
J Org Chem. 2020 Dec 18;85(24):15936-15944. doi: 10.1021/acs.joc.0c01279. Epub 2020 Oct 16.