利用邻基参与实现缩醛的非环立体选择性取代反应中的非对映选择性控制。
Using Neighboring-Group Participation for Acyclic Stereocontrol in Diastereoselective Substitution Reactions of Acetals.
机构信息
Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003, United States.
出版信息
Org Lett. 2020 Jun 5;22(11):4113-4117. doi: 10.1021/acs.orglett.0c01166. Epub 2020 May 11.
Abstract
Neighboring-group participation of an ester enabled stereocontrol in substitution reactions of acyclic acetals. The ester group formed a -fused dioxolenium ion intermediate, which underwent a substitution reaction at the acetal carbon atom to afford the product with high diastereoselectivity. Neighboring-group participation was confirmed by isolating dioxolane products resulting from nucleophilic addition at C-2 of a 1,3-dioxolenium ion intermediate. Using a pivaloate ester as the participating group in combination with strong nucleophiles produced substitution products with diastereoselectivities of ≥90:10.
摘要
酯基的邻基参与实现了非环缩醛取代反应的立体控制。酯基形成了一个 - 稠合的二氧戊环翁离子中间体，该中间体在缩醛碳原子上发生取代反应，以高非对映选择性得到产物。通过分离亲核加成在 1,3-二氧戊环翁离子中间体的 C-2 上得到的二氧杂环戊烷产物，证实了邻基参与。使用特戊酸酯作为参与基团与强亲核试剂结合，得到了非对映选择性≥90:10 的取代产物。
相似文献
1
Using Neighboring-Group Participation for Acyclic Stereocontrol in Diastereoselective Substitution Reactions of Acetals.利用邻基参与实现缩醛的非环立体选择性取代反应中的非对映选择性控制。
Org Lett. 2020 Jun 5;22(11):4113-4117. doi: 10.1021/acs.orglett.0c01166. Epub 2020 May 11.
2
Neighboring-Group Participation by C-2 Acyloxy Groups: Influence of the Nucleophile and Acyl Group on the Stereochemical Outcome of Acetal Substitution Reactions.C-2酰氧基的邻基参与：亲核试剂和酰基对缩醛取代反应立体化学结果的影响
Chemistry. 2023 Oct 13;29(57):e202301894. doi: 10.1002/chem.202301894. Epub 2023 Sep 11.
3
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.
4
Use of an aminosilyllithium for the diastereoselective synthesis of diphenyl oxasilacyclopentane acetals and polyols.使用氨基硅锂进行二苯基氧杂硅环戊烷缩醛和多元醇的非对映选择性合成。
Org Lett. 2003 Nov 13;5(23):4325-7. doi: 10.1021/ol035577a.
5
Investigation of diastereoselective acyclic α-alkoxydithioacetal substitutions involving thiacarbenium intermediates.涉及硫鎓中间体的非对映选择性无环α-烷氧基二硫缩醛取代反应的研究。
J Org Chem. 2014 Nov 7;79(21):10504-25. doi: 10.1021/jo502181a. Epub 2014 Oct 20.
6
Lewis acid-catalyzed ring-opening reactions of semicyclic N,O-acetals possessing an exocyclic nitrogen atom: mechanistic aspect and application to piperidine alkaloid synthesis.具有环外氮原子的半环状N,O-缩醛的路易斯酸催化开环反应：机理研究及在哌啶生物碱合成中的应用
J Am Chem Soc. 2001 Dec 19;123(50):12510-7. doi: 10.1021/ja0170448.
7
Iridium-Catalyzed Enantioselective Allylic Substitution of Aliphatic Esters with Silyl Ketene Acetals as the Ester Enolates.铱催化的手性烯丙基取代反应，用硅基烯酮缩醛作为酯烯醇盐。
Angew Chem Int Ed Engl. 2017 Jul 17;56(30):8887-8891. doi: 10.1002/anie.201704354. Epub 2017 Jun 27.
8
Diastereoselective oxidative α-amination of aliphatic aldehydes catalyzed by iodine: synthesis of syn-γ-hydroxy-α-amino acetals.碘催化的脂肪族醛的对映选择性氧化 α-胺化：顺式-γ-羟基-α-氨基缩醛的合成。
Org Biomol Chem. 2013 Dec 28;11(48):8387-94. doi: 10.1039/c3ob42043d. Epub 2013 Nov 4.
9
Diastereoselective Prins-type reaction of cycloalkenylcyclopropanol silyl ethers and alpha,beta-unsaturated aldehyde acetals.环烯基环丙醇硅醚与α,β-不饱和醛缩醛的非对映选择性普林斯型反应。
J Org Chem. 2007 Oct 12;72(21):7903-8. doi: 10.1021/jo071272o. Epub 2007 Sep 13.
10
Diastereoselective nucleophilic substitution reactions of oxasilacyclopentane acetals: application of the "inside attack" model for reactions of five-membered ring oxocarbenium ions.氧杂硅杂环戊烷缩醛的非对映选择性亲核取代反应：五元环氧鎓离子反应的“内进攻”模型的应用
J Org Chem. 2002 Apr 5;67(7):2056-64. doi: 10.1021/jo010823m.
引用本文的文献
1
Multicomponent Hosomi-Sakurai reaction on chiral, bio-based, alcohols.手性生物基醇的多组分细见-樱井反应
RSC Adv. 2025 May 29;15(23):17897-17905. doi: 10.1039/d5ra03165f.
2
Diastereoselective Substitution Reactions of Acyclic Acetals Controlled by Remote Participation of an Acyloxy Group.由酰氧基远程参与控制的开链缩醛的非对映选择性取代反应
Org Lett. 2024 Dec 13;26(49):10470-10474. doi: 10.1021/acs.orglett.4c03766. Epub 2024 Dec 2.
3
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.
4
Fluorescence Recognition of Hydrazine Driven by Neighboring Group Participation.邻近基团参与驱动的肼的荧光识别
J Fluoresc. 2025 Jun;35(6):4367-4373. doi: 10.1007/s10895-024-03782-x. Epub 2024 Jul 13.
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.
本文引用的文献
1
Characterization of glycosyl dioxolenium ions and their role in glycosylation reactions.糖基二氧烯鎓离子的特性及其在糖基化反应中的作用。
Nat Commun. 2020 May 29;11(1):2664. doi: 10.1038/s41467-020-16362-x.
2
Total Synthesis of the Reported Structure of Stresgenin B Enabled by the Diastereoselective Cyanation of an Oxocarbenium.通过羰正离子的立体选择性氰化反应实现报道的 Stresgenin B 结构的全合成。
Org Lett. 2018 Dec 21;20(24):7798-7802. doi: 10.1021/acs.orglett.8b03219. Epub 2018 Dec 7.
3
Exploiting Synergistic Effects in Organozinc Chemistry for Direct Stereoselective C-Glycosylation Reactions at Room Temperature.利用有机锌化学中的协同效应实现室温下的直接立体选择性C-糖基化反应。
Angew Chem Int Ed Engl. 2018 Aug 13;57(33):10630-10634. doi: 10.1002/anie.201805758. Epub 2018 Jul 5.
4
Remote Asymmetric Induction Reactions using a E, E-Vinylketene Silyl N, O-Acetal and the Wide Range Stereocontrol Strategy for the Synthesis of Polypropionates.使用E，E-乙烯基酮硅基N，O-缩醛的远程不对称诱导反应以及用于合成聚丙酸酯的广泛立体控制策略。
Acc Chem Res. 2018 May 15;51(5):1301-1314. doi: 10.1021/acs.accounts.8b00125. Epub 2018 May 4.
5
Challenges in the Conversion of Manual Processes to Machine-Assisted Syntheses: Activation of Thioglycoside Donors with Aryl(trifluoroethyl)iodonium Triflimide.将手动过程转化为机器辅助合成的挑战：用芳基（三氟乙基）碘𬭩三氟甲磺酸盐激活硫代糖苷供体。
Org Lett. 2018 Feb 2;20(3):800-803. doi: 10.1021/acs.orglett.7b03940. Epub 2018 Jan 16.
6
Participation of alkoxy groups in reactions of acetals: violation of the reactivity/selectivity principle in a Curtin-Hammett kinetic scenario.烷氧基在缩醛反应中的参与：在柯廷-哈米特动力学情形下对反应性/选择性原则的违背
Angew Chem Int Ed Engl. 2015 Oct 5;54(41):12087-90. doi: 10.1002/anie.201503525. Epub 2015 Aug 19.
7
Stereocontrolled 1,2- glycosylation as the driving force of progress in synthetic carbohydrate chemistry.立体控制的1,2-糖基化作为合成碳水化合物化学进展的驱动力。
Chem Sci. 2015 May 1;6(5):2687-2704. doi: 10.1039/C5SC00280J.
8
Investigation of diastereoselective acyclic α-alkoxydithioacetal substitutions involving thiacarbenium intermediates.涉及硫鎓中间体的非对映选择性无环α-烷氧基二硫缩醛取代反应的研究。
J Org Chem. 2014 Nov 7;79(21):10504-25. doi: 10.1021/jo502181a. Epub 2014 Oct 20.
9
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.
10
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.
Zotero 插件