通过 Rh 和 Jacobsen 的胺的协同催化实现醛和炔烃的立体发散偶联。
Stereodivergent Coupling of Aldehydes and Alkynes via Synergistic Catalysis Using Rh and Jacobsen's Amine.
机构信息
Department of Chemistry, University of California , Irvine, California 92697, United States.
出版信息
J Am Chem Soc. 2017 Jan 25;139(3):1029-1032. doi: 10.1021/jacs.6b10680. Epub 2017 Jan 11.
Abstract
We report an enantioselective coupling between α-branched aldehydes and alkynes to generate vicinal quaternary and tertiary carbon stereocenters. The choice of Rh and organocatalyst combination allows for access to all possible stereoisomers with high enantio-, diastereo-, and regioselectivity. Our study highlights the power of catalysis to activate two common functional groups and provide access to divergent stereoisomers and constitutional structures.
摘要
我们报告了一种 α-支链醛和炔烃之间的对映选择性偶联反应，可生成毗邻的季碳和叔碳立体中心。Rh 和有机催化剂组合的选择允许以高对映选择性、非对映选择性和区域选择性获得所有可能的立体异构体。我们的研究强调了催化的力量，它可以激活两个常见的官能团，并提供获得不同立体异构体和构象结构的途径。
相似文献
1
Stereodivergent Coupling of Aldehydes and Alkynes via Synergistic Catalysis Using Rh and Jacobsen's Amine.通过 Rh 和 Jacobsen 的胺的协同催化实现醛和炔烃的立体发散偶联。
J Am Chem Soc. 2017 Jan 25;139(3):1029-1032. doi: 10.1021/jacs.6b10680. Epub 2017 Jan 11.
2
Enantioselective reductive coupling of alkynes and alpha-keto aldehydes via rhodium-catalyzed hydrogenation: an approach to bryostatin substructures.通过铑催化氢化实现炔烃与α-酮醛的对映选择性还原偶联：一种合成苔藓抑素亚结构的方法。
Org Lett. 2006 Mar 2;8(5):891-4. doi: 10.1021/ol052976s.
3
Enantioselective α-vinylation of aldehydes via the synergistic combination of copper and amine catalysis.手性铜-胺协同催化醛的对映选择性α-乙烯基化反应。
J Am Chem Soc. 2012 Jun 6;134(22):9090-3. doi: 10.1021/ja303116v. Epub 2012 May 29.
4
Addition of alkynes to aldehydes and activated ketones catalyzed by rhodium-phosphine complexes.铑-膦配合物催化的炔烃与醛及活性酮的加成反应。
J Org Chem. 2007 Dec 7;72(25):9590-6. doi: 10.1021/jo701643h. Epub 2007 Nov 14.
5
Catalytic asymmetric enyne addition to aldehdyes and Rh(I)-catalyzed stereoselective domino Pauson-Khand/[4 + 2] cycloaddition.手性铑催化的不对称炔烯加成反应醛和[4 + 2]环加成的Pauson-Khand 重排反应的立体选择性。
J Org Chem. 2013 Mar 15;78(6):2256-65. doi: 10.1021/jo3026065. Epub 2013 Jan 23.
6
Copper-catalyzed enantioselective three-component synthesis of optically active propargylamines from aldehydes, amines, and aliphatic alkynes.铜催化由醛、胺和脂肪族炔烃对光学活性炔丙基胺进行对映选择性三组分合成。
Chemistry. 2010 Feb 22;16(8):2360-2. doi: 10.1002/chem.200903550.
7
Rhodium-catalyzed direct annulation of aldehydes with alkynes leading to indenones: proceeding through in situ directing group formation and removal.铑催化的醛与炔烃的直接环化反应生成茚酮：通过原位导向基团的形成和去除进行。
Org Lett. 2013 Sep 20;15(18):4754-7. doi: 10.1021/ol4021145. Epub 2013 Sep 6.
8
The Asymmetric A³(Aldehyde⁻Alkyne⁻Amine) Coupling: Highly Enantioselective Access to Propargylamines.不对称 A³（醛-炔-胺）偶联反应：高对映选择性合成炔丙胺。
Molecules. 2019 Mar 28;24(7):1216. doi: 10.3390/molecules24071216.
9
Rhodium-Catalyzed Enantioselective Hydroamination of Alkynes with Indolines.铑催化的吲哚啉与炔烃的对映选择性氢胺化反应
J Am Chem Soc. 2015 Jul 8;137(26):8392-5. doi: 10.1021/jacs.5b05200. Epub 2015 Jun 29.
10
Rhodium(III)-amine dual catalysis for the oxidative coupling of aldehydes by directed C-H activation: synthesis of phthalides.铑(III)-胺双催化通过导向 C-H 活化的醛氧化偶联：邻苯二甲酸酐的合成。
Org Lett. 2013 Oct 18;15(20):5166-9. doi: 10.1021/ol402145m. Epub 2013 Oct 8.
引用本文的文献
1
Future Trends in Asymmetric Organo-Metal Combined Catalysis.不对称有机金属联合催化的未来趋势
ACS Cent Sci. 2025 Jul 4;11(8):1275-1288. doi: 10.1021/acscentsci.5c00393. eCollection 2025 Aug 27.
2
The stereo-divergent functionalization of alkynes: a comprehensive review.炔烃的立体发散官能团化：综述
RSC Adv. 2025 Apr 17;15(16):12202-12245. doi: 10.1039/d5ra01579k. eCollection 2025 Apr 16.
3
Synergistic Homogeneous Asymmetric Cu Catalysis with Pd Nanoparticle Catalysis in Stereoselective Coupling of Alkynes with Aldimine Esters.钯纳米颗粒催化与协同均相不对称铜催化在炔烃与醛亚胺酯的立体选择性偶联反应中的应用
J Am Chem Soc. 2024 Oct 16;146(41):28427-28436. doi: 10.1021/jacs.4c09983. Epub 2024 Oct 2.
4
Ni/Cu Dual-Catalyzed Propargylation for the Stereodivergent Synthesis of Methohexital.镍/铜双催化炔丙基化反应用于美索比妥的立体发散合成
Adv Sci (Weinh). 2024 Sep;11(36):e2406764. doi: 10.1002/advs.202406764. Epub 2024 Jul 25.
5
Copper/ruthenium relay catalysis enables 1,6-double chiral inductions with stereodivergence.铜/钌接力催化实现了具有立体发散性的1,6-双不对称诱导。
Chem Sci. 2024 May 16;15(26):10135-10145. doi: 10.1039/d4sc01804d. eCollection 2024 Jul 3.
6
Stereodivergent synthesis of α-fluoro α-azaaryl γ-butyrolactones cooperative copper and iridium catalysis.α-氟-α-氮杂芳基-γ-丁内酯的立体发散合成：铜和铱协同催化
Fundam Res. 2022 Jul 29;4(1):77-85. doi: 10.1016/j.fmre.2022.07.008. eCollection 2024 Jan.
7
Catalytic stereodivergent allylic alkylation of 2-acylimidazoles for natural product synthesis.用于天然产物合成的2-酰基咪唑的催化立体发散烯丙基烷基化反应
Nat Commun. 2023 Dec 8;14(1):8118. doi: 10.1038/s41467-023-43986-6.
8
Diastereodivergent Catalysis.非对映发散催化
JACS Au. 2023 Sep 26;3(10):2612-2630. doi: 10.1021/jacsau.3c00216. eCollection 2023 Oct 23.
9
Metal-Catalyzed Enantioconvergent Transformations.金属催化的对映汇聚转化
Chem Rev. 2023 Oct 25;123(20):11817-11893. doi: 10.1021/acs.chemrev.3c00059. Epub 2023 Oct 4.
10
Synthesis of Allenes by Hydroalkylation of 1,3-Enynes with Ketones Enabled by Cooperative Catalysis.通过协同催化实现1,3-烯炔与酮的氢烷基化反应合成丙二烯
J Am Chem Soc. 2023 Oct 4;145(39):21638-21645. doi: 10.1021/jacs.3c08151. Epub 2023 Sep 22.
本文引用的文献
1
Stereodivergent Allylic Substitutions with Aryl Acetic Acid Esters by Synergistic Iridium and Lewis Base Catalysis.铱与路易斯碱协同催化实现芳基乙酸酯的立体发散性烯丙基取代反应
J Am Chem Soc. 2017 Jan 11;139(1):87-90. doi: 10.1021/jacs.6b11692. Epub 2016 Dec 22.
2
Combinations of Aminocatalysts and Metal Catalysts: A Powerful Cooperative Approach in Selective Organic Synthesis.氨基酸催化剂和金属催化剂的组合：选择性有机合成中的一种强大协同方法。
Chem Rev. 2016 Nov 23;116(22):13512-13570. doi: 10.1021/acs.chemrev.6b00226. Epub 2016 Oct 10.
3
Cooperative Palladium/Proline-Catalyzed Direct α-Allylic Alkylation of Ketones with Alkynes.钯/脯氨酸协同催化酮与炔烃的直接 α-烯丙基烷基化反应。
Org Lett. 2016 Oct 21;18(20):5332-5335. doi: 10.1021/acs.orglett.6b02649. Epub 2016 Sep 29.
4
An Ir/Zn Dual Catalysis for Enantio- and Diastereodivergent α-Allylation of α-Hydroxyketones.铱/锌双催化的 α-羟基酮的对映选择性和非对映选择性 α-烯丙基化反应。
J Am Chem Soc. 2016 Sep 7;138(35):11093-6. doi: 10.1021/jacs.6b06156. Epub 2016 Aug 25.
5
Dual Catalysis Using Boronic Acid and Chiral Amine: Acyclic Quaternary Carbons via Enantioselective Alkylation of Branched Aldehydes with Allylic Alcohols.硼酸和手性胺的双重催化：通过支链醛与烯丙醇的对映选择性烷基化反应构建非环状季碳中心。
J Am Chem Soc. 2016 Aug 31;138(34):10762-5. doi: 10.1021/jacs.6b06101. Epub 2016 Aug 17.
6
Branching Out: Rhodium-Catalyzed Allylation with Alkynes and Allenes.支化反应：铑催化的炔烃和烯丙基化反应。
Acc Chem Res. 2016 Aug 16;49(8):1524-36. doi: 10.1021/acs.accounts.6b00252. Epub 2016 Jul 25.
7
Tandem Rh-catalysis: decarboxylative β-keto acid and alkyne cross-coupling.串联铑催化：脱羧β-酮酸与炔烃交叉偶联
Chem Commun (Camb). 2016 Apr 30;52(34):5836-9. doi: 10.1039/c6cc02522f. Epub 2016 Apr 4.
8
Rhodium-catalyzed chemo- and regioselective decarboxylative addition of β-ketoacids to alkynes.铑催化的β-酮酸与炔烃的化学和区域选择性脱羧加成反应。
Chem Commun (Camb). 2016 Apr 30;52(34):5840-3. doi: 10.1039/c6cc02272c. Epub 2016 Apr 4.
9
Copper-catalysed enantioselective stereodivergent synthesis of amino alcohols.铜催化的对映选择性立体发散合成氨基醇。
Nature. 2016 Apr 21;532(7599):353-6. doi: 10.1038/nature17191. Epub 2016 Mar 28.
10
Regioselective Rhodium-Catalyzed Addition of 1,3-Dicarbonyl Compounds to Terminal Alkynes.区域选择性铑催化 1,3-二羰基化合物与末端炔烃的加成反应。
Org Lett. 2016 Jan 4;18(1):124-7. doi: 10.1021/acs.orglett.5b03391. Epub 2015 Dec 18.
Zotero 插件