远程烷氧基对缩醛水解的加速作用：对氧杂碳正离子形成的静电效应的证据。
Acceleration of acetal hydrolysis by remote alkoxy groups: evidence for electrostatic effects on the formation of oxocarbenium ions.
机构信息
Department of Chemistry, New York University, 100 Washington Square East, New York, NY 10003 (USA).
出版信息
Angew Chem Int Ed Engl. 2015 Mar 2;54(10):3061-4. doi: 10.1002/anie.201410043. Epub 2015 Jan 22.
Abstract
In contrast to observations with carbohydrates, experiments with 4-alkoxy-substituted acetals indicate that an alkoxy group can accelerate acetal hydrolysis by up to 20-fold compared to substrates without an alkoxy group. The acceleration of ionization in more flexible acetals can be up to 200-fold when compensated for inductive effects.
摘要
与碳水化合物的观察结果相反，对 4-烷氧基取代的缩醛的实验表明，与没有烷氧基的底物相比，烷氧基可以使缩醛水解加速高达 20 倍。当补偿诱导效应时，更灵活的缩醛的离解加速可以高达 200 倍。
相似文献
1
Acceleration of acetal hydrolysis by remote alkoxy groups: evidence for electrostatic effects on the formation of oxocarbenium ions.远程烷氧基对缩醛水解的加速作用：对氧杂碳正离子形成的静电效应的证据。
Angew Chem Int Ed Engl. 2015 Mar 2;54(10):3061-4. doi: 10.1002/anie.201410043. Epub 2015 Jan 22.
2
Influence of alkoxy groups on rates of acetal hydrolysis and tosylate solvolysis: electrostatic stabilization of developing oxocarbenium ion intermediates and neighboring-group participation to form oxonium ions.烷氧基对缩醛水解速率和对甲苯磺酸酯溶剂解速率的影响：对形成的氧鎓离子中间体的静电稳定作用以及邻基参与以形成氧鎓离子。
J Org Chem. 2015 May 1;80(9):4470-80. doi: 10.1021/acs.joc.5b00338. Epub 2015 Apr 9.
3
Electrostatic effects on the reactions of cyclohexanone oxocarbenium ions.静电对环己酮氧鎓离子反应的影响。
J Org Chem. 2006 Sep 1;71(18):6851-8. doi: 10.1021/jo060968z.
4
The disarming effect of the 4,6-acetal group on glycoside reactivity: torsional or electronic?4,6-缩醛基团对糖苷反应活性的钝化作用：扭转效应还是电子效应？
J Am Chem Soc. 2004 Aug 4;126(30):9205-13. doi: 10.1021/ja047578j.
5
Diastereoselective Substitution Reactions of Acyclic β-Alkoxy Acetals via Electrostatically Stabilized Oxocarbenium Ion Intermediates.通过静电稳定的氧杂羰𬭩离子中间体进行非环β-烷氧基缩醛的立体选择性取代反应。
Org Lett. 2022 May 6;24(17):3217-3222. doi: 10.1021/acs.orglett.2c01004. Epub 2022 Apr 21.
6
Structural evidence that alkoxy substituents adopt electronically preferred pseudoaxial orientations in six-membered ring dioxocarbenium ions.结构证据表明，在六元环二氧碳鎓离子中，烷氧基取代基采取电子学上更有利的假轴向取向。
J Am Chem Soc. 2005 Apr 20;127(15):5322-3. doi: 10.1021/ja050830i.
7
Selective cleavage of methoxy protecting groups in carbohydrates.碳水化合物中甲氧基保护基团的选择性裂解。
J Org Chem. 2006 Mar 3;71(5):1938-48. doi: 10.1021/jo052313o.
8
Investigations into the role of ion pairing in reactions of heteroatom-substituted cyclic oxocarbenium ions.关于离子对在杂原子取代的环状氧鎓离子反应中作用的研究。
Org Lett. 2005 Mar 17;7(6):1157-60. doi: 10.1021/ol0500620.
9
The acid hydrolysis mechanism of acetals catalyzed by a supramolecular assembly in basic solution.在碱性溶液中，超分子组装体催化缩醛的酸水解机理。
J Org Chem. 2009 Jan 2;74(1):58-63. doi: 10.1021/jo802131v.
10
A Ferrier-type allylic rearrangement of 3'-deoxy-3',4'-didehydronucleosides mediated by DMF dimethyl acetal: direct access to 4'-alkoxy-2',3'-didehydro-2',3'-dideoxynucleosides.DMF 二甲缩醛介导的 3'-脱氧-3',4'-二去氢核苷的 Ferrier 型烯丙基重排：直接得到 4'-烷氧基-2',3'-二去氢-2',3'-二脱氧核苷。
Org Lett. 2011 Aug 19;13(16):4200-3. doi: 10.1021/ol201519a. Epub 2011 Jul 18.
引用本文的文献
1
Toward Polymeric Room Temperature Acid Generators.迈向聚合物室温酸发生器。
ChemistryOpen. 2025 Mar;14(3):e202400289. doi: 10.1002/open.202400289. Epub 2024 Nov 26.
2
Acetal Substitution Reactions: Stereoelectronic Effects, Conformational Analysis, Reactivity vs. Selectivity, and Neighboring-Group Participation.缩醛取代反应：立体电子效应、构象分析、反应活性与选择性以及邻基参与作用
Synlett. 2024 Sep;35(15):1763-1787. doi: 10.1055/s-0042-1751541. Epub 2024 Jan 16.
3
Side Chain Conformation and Its Influence on Glycosylation Selectivity in Hexo- and Higher Carbon Furanosides.侧链构象及其对六碳和更高碳呋喃糖苷糖基化选择性的影响。
J Org Chem. 2022 Jan 7;87(1):316-339. doi: 10.1021/acs.joc.1c02374. Epub 2021 Dec 14.
4
Ruthenium-Catalyzed Dehydrogenation Through an Intermolecular Hydrogen Atom Transfer Mechanism.通过分子间氢原子转移机制的钌催化脱氢反应。
Angew Chem Int Ed Engl. 2021 Mar 22;60(13):7290-7296. doi: 10.1002/anie.202015837. Epub 2021 Feb 25.
5
Mechanisms of Stereodirecting Participation and Ester Migration from Near and Far in Glycosylation and Related Reactions.糖基化及相关反应中立体定向参与和酯迁移的近程和远程机制。
Chem Rev. 2020 Aug 12;120(15):7104-7151. doi: 10.1021/acs.chemrev.0c00243. Epub 2020 Jul 5.
6
Chiral Pentacarboxycyclopentadiene-Based Brønsted Acid-Catalyzed Enantioselective Desymmetrization of Meso-Epoxides by 2-Mercaptobenzothiazoles.基于手性五羧基环戊二烯的布朗斯特酸催化2-巯基苯并噻唑对内消旋环氧化合物的对映选择性去对称化反应
ACS Omega. 2018 Jun 25;3(6):6820-6826. doi: 10.1021/acsomega.8b01207. eCollection 2018 Jun 30.
7
Stereoselective organocatalyzed glycosylations - thiouracil, thioureas and monothiophthalimide act as Brønsted acid catalysts at low loadings.立体选择性有机催化糖基化反应——硫脲、硫脲和单硫代邻苯二甲酰亚胺在低负载量下作为布朗斯特酸催化剂。
Chem Sci. 2018 Oct 22;10(2):508-514. doi: 10.1039/c8sc02788a. eCollection 2019 Jan 14.
8
Determination of the Influence of Side-Chain Conformation on Glycosylation Selectivity using Conformationally Restricted Donors.使用构象受限供体确定侧链构象对糖基化选择性的影响
Chemistry. 2016 Mar 18;22(13):4535-42. doi: 10.1002/chem.201505019. Epub 2016 Feb 16.
9
Stereoelectronic Model To Explain Highly Stereoselective Reactions of Seven-Membered-Ring Oxocarbenium-Ion Intermediates.用于解释七元环氧化碳鎓离子中间体高度立体选择性反应的立体电子模型
Angew Chem Int Ed Engl. 2016 Jan 26;55(5):1816-9. doi: 10.1002/anie.201507806. Epub 2016 Jan 6.
10
Absence of Stereodirecting Participation by 2-O-Alkoxycarbonylmethyl Ethers in 4,6-O-Benzylidene-Directed Mannosylation.2-O-烷氧羰基甲基醚在4,6-O-亚苄基定向甘露糖基化反应中不存在立体定向参与作用。
J Org Chem. 2015 Dec 18;80(24):12300-10. doi: 10.1021/acs.joc.5b02203. Epub 2015 Nov 25.
本文引用的文献
1
Nucleophilic addition to silyl-protected five-membered ring oxocarbenium ions governed by stereoelectronic effects.受立体电子效应控制的硅保护的五元环氧杂碳正离子的亲核加成。
J Org Chem. 2013 Jul 5;78(13):6609-21. doi: 10.1021/jo400945j. Epub 2013 Jun 24.
2
Extreme oxatriquinanes and a record C-O bond length.极端氧杂三亚芴烷和创纪录的 C-O 键长。
Nat Chem. 2012 Dec;4(12):1018-23. doi: 10.1038/nchem.1502. Epub 2012 Nov 18.
3
Toward automated oligosaccharide synthesis.朝着自动化寡糖合成的方向发展。
Angew Chem Int Ed Engl. 2011 Dec 9;50(50):11872-923. doi: 10.1002/anie.201100125. Epub 2011 Nov 30.
4
The influence of neighboring group participation on the hydrolysis of 2-O-substituted methyl glucopyranosides.邻基参与对 2-O-取代甲基吡喃葡萄糖苷水解的影响。
Org Lett. 2011 Nov 18;13(22):5956-9. doi: 10.1021/ol202308y. Epub 2011 Oct 18.
5
Neighboring-group participation by C-2 ether functions in glycosylations directed by nitrile solvents.氰基溶剂导向的糖苷化反应中 C-2 醚官能团的邻基参与。
Chemistry. 2011 Oct 17;17(43):12193-202. doi: 10.1002/chem.201100732. Epub 2011 Sep 14.
6
Metal-catalyzed silylene insertions of allylic ethers: stereoselective formation of chiral allylic silanes.金属催化的烯丙基醚的硅烯插入反应：手性烯丙基硅烷的立体选择性形成
J Am Chem Soc. 2007 Oct 24;129(42):12602-3. doi: 10.1021/ja073758s. Epub 2007 Sep 28.
7
Structural evidence that alkoxy substituents adopt electronically preferred pseudoaxial orientations in six-membered ring dioxocarbenium ions.结构证据表明，在六元环二氧碳鎓离子中，烷氧基取代基采取电子学上更有利的假轴向取向。
J Am Chem Soc. 2005 Apr 20;127(15):5322-3. doi: 10.1021/ja050830i.
8
The disarming effect of the 4,6-acetal group on glycoside reactivity: torsional or electronic?4,6-缩醛基团对糖苷反应活性的钝化作用：扭转效应还是电子效应？
J Am Chem Soc. 2004 Aug 4;126(30):9205-13. doi: 10.1021/ja047578j.
9
Stereocontrol of 1,5-related stereocentres using an intermediate silyl group--the diastereoselectivity of nucleophilic attack on a double bond adjacent to a stereogenic centre carrying a silyl group.利用中间体硅基对1,5-相关立体中心进行立体控制——对与带有硅基的立体中心相邻的双键进行亲核进攻的非对映选择性。
Org Biomol Chem. 2003 Nov 21;1(22):3989-4004. doi: 10.1039/b305880h.
10
Steric effects are not the cause of the rate difference in hydrolysis of stereoisomeric glycosides.空间效应不是立体异构糖苷水解速率差异的原因。
Org Lett. 2003 Sep 18;5(19):3419-21. doi: 10.1021/ol030081e.
Zotero 插件