• 文献检索
  • 文档翻译
  • 深度研究
  • 学术资讯
  • Suppr Zotero 插件Zotero 插件
  • 邀请有礼
  • 套餐&价格
  • 历史记录
应用&插件
Suppr Zotero 插件Zotero 插件浏览器插件Mac 客户端Windows 客户端微信小程序
定价
高级版会员购买积分包购买API积分包
服务
文献检索文档翻译深度研究API 文档MCP 服务
关于我们
关于 Suppr公司介绍联系我们用户协议隐私条款
关注我们

Suppr 超能文献

核心技术专利：CN118964589B侵权必究
粤ICP备2023148730 号-1Suppr @ 2026

文献检索

告别复杂PubMed语法，用中文像聊天一样搜索，搜遍4000万医学文献。AI智能推荐，让科研检索更轻松。

立即免费搜索

文件翻译

保留排版，准确专业，支持PDF/Word/PPT等文件格式，支持 12+语言互译。

免费翻译文档

深度研究

AI帮你快速写综述，25分钟生成高质量综述，智能提取关键信息，辅助科研写作。

立即免费体验

克级碳糖合成中的分子内迈克尔/羟醛反应。

Gram-scale carbasugar synthesis intramolecular -Michael/aldol reaction.

作者信息

Banachowicz Piotr, Buda Szymon

机构信息

Faculty of Chemistry, Jagiellonian University Gronostajowa 2 30-387 Krakow Poland

出版信息

RSC Adv. 2019 Apr 26;9(23):12928-12935. doi: 10.1039/c9ra02002k. eCollection 2019 Apr 25.

DOI:10.1039/c9ra02002k
PMID:35520757
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9063748/
Abstract

Carbasugars represent an important category of natural products possessing a broad spectrum of biological activities. Lots of effort has been done to develop gram scale synthesis. We are presenting a new approach to gram scale synthesis of the carbasugar skeleton intramolecular -Michael/aldol reaction. The proposed strategy gave gram amounts of 6-hydroxy shikimic ester in a tandem process in 36% overall yield starting from d-lyxose. We have attempted to demonstrate the synthetic utility of 6-hydroxyshikimic acid derivatives by covering the important synthetic modifications and related applications, namely synthesis of protected (-)-gabosine E, (-)-MK7606, (-)-valienamine and finally unprotected methyl (-)-shikimate.

摘要

碳环糖是一类具有广泛生物活性的重要天然产物。人们为开发克级规模的合成方法付出了诸多努力。我们正在展示一种通过分子内迈克尔/羟醛反应进行碳环糖骨架克级规模合成的新方法。所提出的策略从D-来苏糖开始，通过串联过程以36%的总收率得到克级量的6-羟基莽草酸酯。我们试图通过涵盖重要的合成修饰和相关应用来证明6-羟基莽草酸衍生物的合成效用，即合成保护的(-)-加波辛E、(-)-MK7606、(-)-缬氨霉素，最后合成未保护的(-)-莽草酸甲酯。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a3f2/9063748/02306e91c4ab/c9ra02002k-s5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a3f2/9063748/395ffcfa9d0a/c9ra02002k-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a3f2/9063748/f5f5cf794da0/c9ra02002k-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a3f2/9063748/89428b1d252a/c9ra02002k-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a3f2/9063748/6ca0fa2b56a0/c9ra02002k-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a3f2/9063748/02306e91c4ab/c9ra02002k-s5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a3f2/9063748/395ffcfa9d0a/c9ra02002k-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a3f2/9063748/f5f5cf794da0/c9ra02002k-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a3f2/9063748/89428b1d252a/c9ra02002k-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a3f2/9063748/6ca0fa2b56a0/c9ra02002k-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a3f2/9063748/02306e91c4ab/c9ra02002k-s5.jpg

相似文献

1
Gram-scale carbasugar synthesis intramolecular -Michael/aldol reaction.克级碳糖合成中的分子内迈克尔/羟醛反应。
RSC Adv. 2019 Apr 26;9(23):12928-12935. doi: 10.1039/c9ra02002k. eCollection 2019 Apr 25.
2
A Synthetic Approach to Several C7-Carbasugars via a Key Intramolecular Morita-Baylis-Hillman Reaction.通过关键的分子内 Morita-Baylis-Hillman 反应合成几种 C7-碳环糖。
J Org Chem. 2022 Nov 4;87(21):14636-14645. doi: 10.1021/acs.joc.2c01992. Epub 2022 Oct 12.
3
Carbasugar Synthesis via Vinylogous Ketal: Total Syntheses of (+)-MK7607, (-)-MK7607, (-)-Gabosine A, (-)-Epoxydine B, (-)-Epoxydine C, epi-(+)-Gabosine E and epi-(+)-MK7607.通过乙烯酮缩醛化合成碳糖：(+)-MK7607、(-)-MK7607、(-)-Gabosine A、(-)-Epoxydine B、(-)-Epoxydine C、epi-(+)-Gabosine E 和 epi-(+)-MK7607 的全合成。
J Org Chem. 2016 Dec 2;81(23):11635-11645. doi: 10.1021/acs.joc.6b01876. Epub 2016 Nov 10.
4
A divergent strategy to synthesize gabosines featuring a switchable two-way aldol cyclization.一种采用可切换双向羟醛缩合反应来合成 gabosines 的发散策略。
Org Biomol Chem. 2019 Apr 17;17(16):4061-4072. doi: 10.1039/c9ob00469f.
5
Total Syntheses of (+)-Gabosine P, (+)-Gabosine Q, (+)-Gabosine E, (-)-Gabosine G, (-)-Gabosine I, (-)-Gabosine K, (+)-Streptol, and (-)-Uvamalol A by a Diversity-Oriented Approach Featuring Tunable Deprotection Manipulation.采用多样化导向方法，通过可调去保护操作实现 (+)-Gabosine P、(+)-Gabosine Q、(+)-Gabosine E、(-)-Gabosine G、(-)-Gabosine I、(-)-Gabosine K、(+)-Streptol 和 (-)-Uvamalol A 的全合成。
J Org Chem. 2017 Apr 7;82(7):3692-3701. doi: 10.1021/acs.joc.7b00181. Epub 2017 Mar 20.
6
Intramolecular Tandem Seleno-Michael/Aldol Reaction: A Simple Route to Hydroxy Cyclo-1-ene-1-carboxylate Esters.分子内串联硒代-迈克尔/羟醛反应：合成羟基环-1-烯-1-羧酸酯的简便途径。
J Org Chem. 2018 Sep 21;83(18):11269-11277. doi: 10.1021/acs.joc.8b01853. Epub 2018 Aug 20.
7
Oxocarbenium ion cyclizations for the synthesis of disaccharide mimetics of 2-amino-2-deoxy-pyranosides: Application to the carbasugar of β-galactosamine-(1,4)-3-O-methyl-D-chiro-inositol.氧杂碳鎓离子环化反应在 2-氨基-2-脱氧吡喃糖类似物二糖的合成中的应用：在β-半乳糖胺-(1,4)-3-O-甲基-D-手性肌醇的碳环糖中的应用。
Carbohydr Res. 2022 Aug;518:108595. doi: 10.1016/j.carres.2022.108595. Epub 2022 May 23.
8
Vinylogy in orthoester hydrolysis: total syntheses of cyclophellitol, valienamine, gabosine K, valienone, gabosine G, 1-epi-streptol, streptol, and uvamalol A.乙烯基环酯水解中的 vinylogy：环磷醇、戊烯胺、加波沙因 K、戊烯酮、加波沙因 G、1-表链霉醇、链霉醇和乌伐马洛 A 的全合成。
J Org Chem. 2013 Aug 2;78(15):7690-700. doi: 10.1021/jo401272j. Epub 2013 Jul 24.
9
Total Synthesis of a PPAP, Nemorosonol, Using a Tandem Michael Addition-Intramolecular Aldol Reaction.利用串联迈克尔加成-分子内Aldol 反应全合成 PPAP、Nemorosonol
Org Lett. 2022 Jul 1;24(25):4635-4639. doi: 10.1021/acs.orglett.2c01745. Epub 2022 Jun 15.
10
NHC-Catalyzed Generation of α,β-Unsaturated Acylazoliums for the Enantioselective Synthesis of Heterocycles and Carbocycles.NHC 催化生成 α,β-不饱和酰基氮鎓盐用于杂环和碳环的对映选择性合成。
Acc Chem Res. 2019 Feb 19;52(2):425-436. doi: 10.1021/acs.accounts.8b00550. Epub 2019 Jan 17.

引用本文的文献

1
Elucidation of the acid reactivity of polyhedral orthoformates for the synthesis of carbasugar derivatives.用于合成碳环糖衍生物的多聚原酸酯的酸反应性解析
RSC Adv. 2025 Jun 19;15(26):20734-20744. doi: 10.1039/d5ra01049g. eCollection 2025 Jun 16.
2
General strategy for the synthesis of unsaturated carbasugars a diastereoselective -Michael/aldol reaction.合成不饱和碳环糖的通用策略——非对映选择性迈克尔/羟醛反应。
RSC Adv. 2025 Feb 18;15(7):5159-5166. doi: 10.1039/d5ra00322a. eCollection 2025 Feb 13.
3
Diverse Library of 5a-Substituted Carba-Glucosamines.

本文引用的文献

1
A divergent strategy to synthesize gabosines featuring a switchable two-way aldol cyclization.一种采用可切换双向羟醛缩合反应来合成 gabosines 的发散策略。
Org Biomol Chem. 2019 Apr 17;17(16):4061-4072. doi: 10.1039/c9ob00469f.
2
Synthesis of 5a,5a'-dicarba-d-glucobioses from conformationally restricted carbaglucosyl triflates using S2-type inversion with carbaglucosyl nucleophiles.用 S2 型反转与碳苷亲核试剂从构象受限的碳苷三氟甲磺酸酯合成 5a,5a'-二碳代-d-吡喃葡萄糖苷。
Bioorg Med Chem. 2019 Jun 15;27(12):2345-2367. doi: 10.1016/j.bmc.2018.12.027. Epub 2018 Dec 19.
3
Allylic Strain as a Stereocontrol Element in the Hydrogenation of 3-Hydroxymethyl-cyclohex-3-en-1,2,5-triol Derivatives. Synthesis of the Carbasugar Pseudo-2-deoxy-α-D-glucopyranose.
5a-取代碳环葡糖胺的多样文库。
J Org Chem. 2025 Feb 28;90(8):2969-2977. doi: 10.1021/acs.joc.4c02816. Epub 2025 Feb 15.
4
Chemoselective Nozaki-Hiyama-Takai-Kishi and Grignard reaction: short synthesis of some carbahexopyranoses.化学选择性的野崎-日山-高井-岸反应及格氏反应：某些碳杂己吡喃糖的简短合成
RSC Adv. 2023 Jul 28;13(33):22824-22830. doi: 10.1039/d3ra03704e. eCollection 2023 Jul 26.
5
Synergy of R-(-)carvone and cyclohexenone-based carbasugar precursors with antibiotics to enhance antibiotic potency and inhibit biofilm formation.（-）香芹酮和基于环己烯酮的碳环糖前体与抗生素协同作用，增强抗生素效力并抑制生物膜形成。
Sci Rep. 2022 Oct 26;12(1):18019. doi: 10.1038/s41598-022-22807-8.
6
Heparan Sulfate, Mucopolysaccharidosis IIIB and Sulfur Metabolism Disorders.硫酸乙酰肝素、黏多糖贮积症IIIB与硫代谢紊乱
Antioxidants (Basel). 2022 Mar 30;11(4):678. doi: 10.3390/antiox11040678.
7
Current Synthetic Approaches to the Synthesis of Carbasugars from Non-Carbohydrate Sources.当前从非碳水化合物源合成碳环糖的合成方法。
Top Curr Chem (Cham). 2022 Feb 9;380(2):12. doi: 10.1007/s41061-022-00370-0.
烯丙基张力作为3-羟甲基-环己-3-烯-1,2,5-三醇衍生物氢化反应中的立体控制元素。碳环糖伪-2-脱氧-α-D-葡萄糖吡喃糖的合成。
Tetrahedron. 2018 Sep 20;74(38):5183-5191. doi: 10.1016/j.tet.2018.04.078. Epub 2018 Apr 30.
4
Production and Synthetic Modifications of Shikimic Acid.莽草酸的生产与合成修饰
Chem Rev. 2018 Oct 24;118(20):10458-10550. doi: 10.1021/acs.chemrev.8b00350. Epub 2018 Oct 11.
5
Revealing the mechanism for covalent inhibition of glycoside hydrolases by carbasugars at an atomic level.在原子水平上揭示碳杂糖对半乳糖苷水解酶的共价抑制机制。
Nat Commun. 2018 Aug 13;9(1):3243. doi: 10.1038/s41467-018-05702-7.
6
Intramolecular Tandem Seleno-Michael/Aldol Reaction: A Simple Route to Hydroxy Cyclo-1-ene-1-carboxylate Esters.分子内串联硒代-迈克尔/羟醛反应：合成羟基环-1-烯-1-羧酸酯的简便途径。
J Org Chem. 2018 Sep 21;83(18):11269-11277. doi: 10.1021/acs.joc.8b01853. Epub 2018 Aug 20.
7
New Class of Glycoside Hydrolase Mechanism-Based Covalent Inhibitors: Glycosylation Transition State Conformations.新型糖苷水解酶基于机制的共价抑制剂类别：糖基化过渡态构象。
J Am Chem Soc. 2017 Aug 9;139(31):10625-10628. doi: 10.1021/jacs.7b05065. Epub 2017 Jul 26.
8
Stereoselective Synthesis and Evaluation of C6″-Substituted 5a-Carbasugar Analogues of SL0101 as Inhibitors of RSK1/2.C6″-取代 5a-碳环糖类似物作为 RSK1/2 抑制剂的立体选择性合成与评价。
Org Lett. 2017 May 5;19(9):2410-2413. doi: 10.1021/acs.orglett.7b00945. Epub 2017 Apr 25.
9
Total Syntheses of (+)-Gabosine P, (+)-Gabosine Q, (+)-Gabosine E, (-)-Gabosine G, (-)-Gabosine I, (-)-Gabosine K, (+)-Streptol, and (-)-Uvamalol A by a Diversity-Oriented Approach Featuring Tunable Deprotection Manipulation.采用多样化导向方法，通过可调去保护操作实现 (+)-Gabosine P、(+)-Gabosine Q、(+)-Gabosine E、(-)-Gabosine G、(-)-Gabosine I、(-)-Gabosine K、(+)-Streptol 和 (-)-Uvamalol A 的全合成。
J Org Chem. 2017 Apr 7;82(7):3692-3701. doi: 10.1021/acs.joc.7b00181. Epub 2017 Mar 20.
10
Toward synthesis of carbasugars (+)-gabosine C, (+)-COTC, (+)-pericosine B, and (+)-pericosine C.为了合成 carbasugars（+）-gabosine C、（+）-COTC、（+）-pericosine B 和（+）-pericosine C。
Carbohydr Res. 2014 Mar 31;388:130-7. doi: 10.1016/j.carres.2013.08.008. Epub 2013 Aug 20.