源自HDDA的苯炔与硫化物的反应：机理、模式及三组分反应
Reactions of HDDA-Derived Benzynes with Sulfides: Mechanism, Modes, and Three-Component Reactions.
作者信息
Chen Junhua, Palani Vignesh, Hoye Thomas R
机构信息
Department of Chemistry, University of Minnesota , 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
出版信息
J Am Chem Soc. 2016 Apr 6;138(13):4318-21. doi: 10.1021/jacs.6b01025. Epub 2016 Mar 28.
Abstract
We report here reactions of alkyl sulfides with benzynes thermally generated by the hexadehydro-Diels-Alder (HDDA) cycloisomerization. The initially produced 1,3-betaine (o-sulfonium/aryl carbanion) undergoes intramolecular proton transfer to generate a more stable S-aryl sulfur ylide. This can react in various manners, including engaging weak acids (HA) in the reaction medium. This can produce transient ion pairs ArSR2(+)A(-) that proceed to the products ArSR + RA. When cyclic sulfides are used, A(-) opens the ring and is incorporated into the product, an outcome that constitutes a versatile, three-component coupling process.
摘要
我们在此报告了烷基硫化物与通过六脱氢狄尔斯-阿尔德（HDDA）环异构化热生成的苯炔的反应。最初生成的1,3-内盐（邻硫鎓/芳基碳负离子）发生分子内质子转移，生成更稳定的S-芳基硫叶立德。它可以以多种方式反应，包括与反应介质中的弱酸（HA）发生反应。这会产生瞬态离子对ArSR2(+)A(-)，进而生成产物ArSR + RA。当使用环状硫化物时，A(-)会打开环并并入产物中，这一结果构成了一种通用的三组分偶联过程。
相似文献
1
Reactions of HDDA-Derived Benzynes with Sulfides: Mechanism, Modes, and Three-Component Reactions.源自HDDA的苯炔与硫化物的反应：机理、模式及三组分反应
J Am Chem Soc. 2016 Apr 6;138(13):4318-21. doi: 10.1021/jacs.6b01025. Epub 2016 Mar 28.
2
Photochemical Hexadehydro-Diels-Alder Reaction.光化学十六氢-狄尔斯-阿尔德反应。
J Am Chem Soc. 2017 Jun 28;139(25):8400-8403. doi: 10.1021/jacs.7b03832. Epub 2017 Jun 20.
3
Reactions of Hexadehydro-Diels-Alder (HDDA)-Derived Benzynes with Thioamides: Synthesis of Dihydrobenzothiazino-Heterocyclics.十六氢-Diels-Alder（HDDA）衍生苯炔与硫代酰胺的反应：二氢苯并噻嗪杂环的合成。
Org Lett. 2016 Dec 16;18(24):6312-6315. doi: 10.1021/acs.orglett.6b03199. Epub 2016 Dec 1.
4
Intramolecular [4 + 2] trapping of a hexadehydro-Diels-Alder (HDDA) benzyne by tethered arenes.通过连接的芳烃对六脱氢狄尔斯-阿尔德（HDDA）苯炔进行分子内[4 + 2]捕获。
Org Lett. 2015 Feb 20;17(4):856-9. doi: 10.1021/ol5037024. Epub 2015 Feb 11.
5
Reactions of HDDA-Derived Benzynes with Perylenes: Rapid Construction of Polycyclic Aromatic Compounds.HDDA 衍生苯炔与苝的反应：多环芳烃化合物的快速构建。
Org Lett. 2016 Nov 4;18(21):5636-5639. doi: 10.1021/acs.orglett.6b02878. Epub 2016 Oct 21.
6
The Phenol-Ene Reaction: Biaryl Synthesis via Trapping Reactions between HDDA-Generated Benzynes and Phenolics.酚烯反应：通过 HDDA 生成的苯炔与酚类化合物之间的捕获反应合成联苯。
Org Lett. 2016 Nov 4;18(21):5596-5599. doi: 10.1021/acs.orglett.6b02830. Epub 2016 Oct 21.
7
Hexadehydro-Diels-Alder Reaction: Benzyne Generation via Cycloisomerization of Tethered Triynes.六脱氢狄尔斯-阿尔德反应：通过连接的三炔的环异构化生成苯炔
Chem Rev. 2021 Feb 24;121(4):2413-2444. doi: 10.1021/acs.chemrev.0c00825. Epub 2021 Jan 25.
8
Mechanistic Duality in Tertiary Amine Additions to Thermally Generated Hexadehydro-Diels-Alder Benzynes.三级胺对热生成的十六氢二苯并[def,mn]薁炔的加成的机理双重性。
Org Lett. 2017 Oct 20;19(20):5705-5708. doi: 10.1021/acs.orglett.7b02888. Epub 2017 Oct 5.
9
Reactions of hexadehydro-Diels-Alder benzynes with structurally complex multifunctional natural products.十六氢-Diels-Alder 苯炔与结构复杂的多功能天然产物的反应。
Nat Chem. 2017 Jun;9(6):523-530. doi: 10.1038/nchem.2732. Epub 2017 Feb 27.
10
The pentadehydro-Diels-Alder reaction.五脱氢狄尔斯-阿尔德反应。
Nature. 2016 Apr 28;532(7600):484-8. doi: 10.1038/nature17429. Epub 2016 Apr 18.
引用本文的文献
1
Acid-catalyzed, Three-component, Spontaneous Cascades of 1,3-Butadiynyl Propargylic Alcohols as a Route to Phthalan Derivatives.酸催化的1,3-丁二炔基炔丙醇的三组分自发级联反应：一种合成酞嗪衍生物的方法
ACS Catal. 2025 Jul 18;15(14):12238-12246. doi: 10.1021/acscatal.5c03571. Epub 2025 Jul 6.
2
An Untethered and Formal Intermolecular Hexadehydro-Diels-Alder Reaction: Alkynylboronates with 2-(1,3-Butadiynyl)pyridines.一种无束缚且形式上的分子间六脱氢狄尔斯-阿尔德反应：硼酸炔酯与2-(1,3-丁二炔基)吡啶的反应
J Am Chem Soc. 2024 Dec 18;146(50):34510-34516. doi: 10.1021/jacs.4c11622. Epub 2024 Dec 6.
3
Generation of Quaternary Carbons in Cycloalkanones and Lactones with Arynes through a Domino Process.通过多米诺过程利用芳炔在环烷酮和内酯中生成季碳。
J Org Chem. 2024 Dec 20;89(24):18393-18399. doi: 10.1021/acs.joc.4c02257. Epub 2024 Nov 30.
4
Benzyne-Promoted, 1,2--Selective -Glycosylation with Benzylchalcogenoglycoside Donors.苯炔促进的苄基硫属糖基供体的1,2-选择性α-糖基化反应
Org Lett. 2023 Dec 1;25(47):8526-8529. doi: 10.1021/acs.orglett.3c03502. Epub 2023 Nov 16.
5
Sulfonium-based precise alkyl transposition reactions.基于锍鎓盐的精确烷基移位反应。
Sci Adv. 2023 Sep 15;9(37):eadi1370. doi: 10.1126/sciadv.adi1370.
6
1,3-Butadiynamides the Ethynylogous Ynamides: Synthesis, Properties and Applications in Heterocyclic Chemistry.1,3-丁二炔酰胺：乙炔基取代的炔酰胺、合成、性质及在杂环化学中的应用。
Molecules. 2023 Jun 5;28(11):4564. doi: 10.3390/molecules28114564.
7
Empowering boronic acids as hydroxyl synthons for aryne induced three-component coupling reactions.使硼酸作为羟基合成子用于芳炔引发的三组分偶联反应。
Chem Sci. 2023 Mar 14;14(16):4278-4287. doi: 10.1039/d3sc00072a. eCollection 2023 Apr 26.
8
Development of an Allenyne-Alkyne [4+2] Cycloaddition and its Application to Total Synthesis of Selaginpulvilin A.烯炔[4+2]环加成反应的开发及其在卷柏素 A 全合成中的应用。
Chemistry. 2022 Oct 7;28(56):e202202015. doi: 10.1002/chem.202202015. Epub 2022 Aug 3.
9
Sequential cycloaddition and ring expansion reaction of arynes and methylenebenzothiopheneones: synthesis of a benzo-fused eight-membered ring sulfonium ylides.芳炔与亚甲基苯并噻吩酮的顺序环加成和扩环反应：苯并稠合八元环锍叶立德的合成
RSC Adv. 2019 Nov 29;9(67):39119-39123. doi: 10.1039/c9ra09332j. eCollection 2019 Nov 27.
10
Radial hexadehydro-Diels-Alder reactions.径向六脱氢狄尔斯-阿尔德反应
Chem. 2021 Sep 9;7(9):2527-2537. doi: 10.1016/j.chempr.2021.08.010.
本文引用的文献
1
Synthesis of N-Aryl β-Amino Alcohols by Trifluoroacetic Acid Promoted Multicomponent Coupling of Aziridines, Arynes, and Water.三氟乙酸促进氮杂环丙烷、芳炔和水的多组分偶联合成N-芳基β-氨基醇
J Org Chem. 2015 Nov 6;80(21):11131-7. doi: 10.1021/acs.joc.5b01798. Epub 2015 Oct 15.
2
Synthesis of Phenolic Compounds by Trapping Arynes with a Hydroxy Surrogate.通过用羟基替代物捕获芳炔合成酚类化合物。
Molecules. 2015 Aug 31;20(9):15862-80. doi: 10.3390/molecules200915862.
3
Mechanism of the Intramolecular Hexadehydro-Diels-Alder Reaction.分子内六脱氢狄尔斯-阿尔德反应的机理
J Org Chem. 2015 Dec 4;80(23):11744-54. doi: 10.1021/acs.joc.5b01356. Epub 2015 Aug 25.
4
Hydroboration of Arynes Formed by Hexadehydro-Diels-Alder Cyclizations with N-Heterocyclic Carbene Boranes.偕二聚环戊二烯与 N-杂环卡宾硼烷形成的芳炔的硼氢化反应。
Org Lett. 2015 Jul 17;17(14):3450-3. doi: 10.1021/acs.orglett.5b01480. Epub 2015 Jun 26.
5
Competition between classical and hexadehydro-Diels-Alder (HDDA) reactions of HDDA triynes with furan.HDDA三炔与呋喃的经典反应和六脱氢狄尔斯-阿尔德（HDDA）反应之间的竞争
Tetrahedron Lett. 2015 Jun 3;56(23):3265-3267. doi: 10.1016/j.tetlet.2014.12.053.
6
Benzannulation of triynes to generate functionalized arenes by spontaneous incorporation of nucleophiles.三炔的苯并环化反应，通过自发掺入亲核试剂来生成官能化芳烃。
Angew Chem Int Ed Engl. 2015 May 26;54(22):6582-6. doi: 10.1002/anie.201412468. Epub 2015 Apr 16.
7
Straightforward synthesis of 5-bromopenta-2,4-diynenitrile and its reactivity towards terminal alkynes: a direct access to diene and benzofulvene scaffolds.5-溴戊-2,4-二炔腈的简便合成及其对末端炔烃的反应性：直接构建二烯和苯并富烯骨架
Chemistry. 2015 Apr 13;21(16):6042-7. doi: 10.1002/chem.201500633. Epub 2015 Mar 11.
8
Intramolecular [4 + 2] trapping of a hexadehydro-Diels-Alder (HDDA) benzyne by tethered arenes.通过连接的芳烃对六脱氢狄尔斯-阿尔德（HDDA）苯炔进行分子内[4 + 2]捕获。
Org Lett. 2015 Feb 20;17(4):856-9. doi: 10.1021/ol5037024. Epub 2015 Feb 11.
9
Differential scanning calorimetry (DSC) as a tool for probing the reactivity of polyynes relevant to hexadehydro-Diels-Alder (HDDA) cascades.差示扫描量热法（DSC）作为一种探测与六脱氢狄尔斯-阿尔德（HDDA）级联反应相关的聚炔反应活性的工具。
Org Lett. 2014 Dec 19;16(24):6370-3. doi: 10.1021/ol503162k. Epub 2014 Dec 3.
10
Tactics for Probing Aryne Reactivity: Mechanistic Studies of Silicon-oxygen Bond Cleavage During the Trapping of (HDDA-generated) Benzynes by Silyl Ethers.探索芳烃反应活性的策略：硅醚捕获（由六元环二烯加成反应生成的）苯炔过程中硅-氧键断裂的机理研究
Chem Sci. 2014 Feb;5(2):545-550. doi: 10.1039/C3SC53014K.
Zotero 插件