不对称催化乙醛的炔丙基化反应：在(+)-四氢扁柏酚合成中的应用。
Asymmetric catalytic alkynylation of acetaldehyde: application to the synthesis of (+)-tetrahydropyrenophorol.
机构信息
Department of Chemistry, University of Stanford, Stanford, CA 94035-5080, USA.
出版信息
Angew Chem Int Ed Engl. 2012 Jul 2;51(27):6704-8. doi: 10.1002/anie.201203035. Epub 2012 Jun 5.
Abstract
[Image: see text] By controlling the kinetics of alkynylation over aldolisation (by slowing adding the acceptor), the challenging asymmetric catalytic alkynylation of acetaldehyde has been realized. This protocol yields the corresponding attractive synthons in good to excellent enantiocontrol and shows broad tolerance and applicability. This was highlighted by its application to the synthesis of several natural products such as the rapid construction of the macrocyclic diolide (+)-tetrahydropyrenophorol.
摘要
[图像：见正文] 通过控制炔丙基化相对于羟醛缩合的动力学（通过缓慢添加受体），实现了具有挑战性的乙醛不对称催化炔丙基化。该方案以良好到优异的对映选择性得到相应的吸引人的合成子，并表现出广泛的耐受性和适用性。该方法的应用突出体现在几种天然产物的合成中，例如大环二醇（+）-四氢罂粟醇的快速构建。
相似文献
1
Asymmetric catalytic alkynylation of acetaldehyde: application to the synthesis of (+)-tetrahydropyrenophorol.不对称催化乙醛的炔丙基化反应：在(+)-四氢扁柏酚合成中的应用。
Angew Chem Int Ed Engl. 2012 Jul 2;51(27):6704-8. doi: 10.1002/anie.201203035. Epub 2012 Jun 5.
2
Asymmetric catalytic synthesis of the proposed structure of trocheliophorolide B.不对称催化合成拟 trocheliophorolide B 的结构。
Org Lett. 2012 Sep 7;14(17):4698-700. doi: 10.1021/ol302074h. Epub 2012 Aug 22.
3
Multi-step synthesis by using modular flow reactors: the preparation of yne--ones and their use in heterocycle synthesis.使用模块化流动反应器的多步合成：炔酮的制备及其在杂环合成中的应用。
Chemistry. 2010 Jan 4;16(1):89-94. doi: 10.1002/chem.200902906.
4
Asymmetric synthesis of D-ribo-phytosphingosine from 1-tetradecyne and (4-methoxyphenoxy)acetaldehyde.从 1-十四炔和（4-甲氧基苯氧基）乙醛不对称合成 D-赤式-植鞘氨醇。
J Org Chem. 2010 Jul 2;75(13):4356-64. doi: 10.1021/jo100707d.
5
Asymmetric catalytic conjugate addition of acetaldehyde to nitrodienynes/nitroenynes: applications to the syntheses of (+)-α-lycorane and chiral β-alkynyl acids.不对称催化的乙醛与硝二烯/硝烯炔的共轭加成：应用于 (+)-α-石蒜碱和手性 β-炔基酸的合成。
Org Lett. 2014 Jun 6;16(11):3044-7. doi: 10.1021/ol501158b. Epub 2014 May 8.
6
Catalytic asymmetric reductive coupling of alkynes and aldehydes: enantioselective synthesis of allylic alcohols and alpha-hydroxy ketones.炔烃与醛的催化不对称还原偶联：烯丙醇和α-羟基酮的对映选择性合成
J Am Chem Soc. 2003 Mar 26;125(12):3442-3. doi: 10.1021/ja034366y.
7
Asymmetric alkynylation of seven-membered cyclic imines by combining chiral phosphoric acids and Ag(I) catalysts: synthesis of 11-substituted-10,11-dihydrodibenzo[b,f][1,4]oxazepine derivatives.通过手性磷酸与Ag(I)催化剂相结合实现七元环亚胺的不对称炔基化反应：11-取代-10,11-二氢二苯并[b,f][1,4]恶唑并氮杂卓衍生物的合成
J Org Chem. 2014 Dec 5;79(23):11759-67. doi: 10.1021/jo5022037. Epub 2014 Nov 14.
8
Stereoselective total synthesis of C-symmetric natural products pyrenophorol and its derivatives.对映选择性全合成 C-对称天然产物苝酚及其衍生物。
Nat Prod Res. 2020 Aug;34(15):2173-2178. doi: 10.1080/14786419.2019.1577843. Epub 2019 Mar 1.
9
Asymmetric addition of 1-ethynylcyclohexene to both aromatic and heteroaromatic ketones catalyzed by a chiral Schiff base-zinc complex.手性席夫碱-锌配合物催化1-乙炔基环己烯对芳香族和杂芳香族酮的不对称加成反应。
Org Biomol Chem. 2007 Apr 21;5(8):1161-3. doi: 10.1039/b702069d. Epub 2007 Mar 9.
10
Highly regioselective, catalytic asymmetric reductive coupling of 1,3-enynes and ketones.1,3-烯炔与酮的高度区域选择性催化不对称还原偶联反应。
Org Lett. 2005 Jul 7;7(14):3077-80. doi: 10.1021/ol051075g.
引用本文的文献
1
Enantioselective Zn-catalyzed hydrophosphinylation of nitrones: an efficient approach for constructing chiral α-hydroxyamino-phosphine oxides.锌催化的硝酮对映选择性氢膦酰化反应：构建手性α-羟基氨基氧化膦的有效方法。
Chem Sci. 2025 Mar 18;16(16):7051-7056. doi: 10.1039/d5sc01453k. eCollection 2025 Apr 16.
2
Simmons-Smith Cyclopropanation: A Multifaceted Synthetic Protocol toward the Synthesis of Natural Products and Drugs: A Review.西蒙斯-史密斯环丙烷化反应：一种多方面的合成方法，用于合成天然产物和药物：综述。
Molecules. 2023 Jul 26;28(15):5651. doi: 10.3390/molecules28155651.
3
Catalytic enantioselective synthesis of macrodiolides and their application in chiral recognition.大环二内酯的催化对映选择性合成及其在手性识别中的应用。
Chem Sci. 2020 Dec 27;12(8):2940-2947. doi: 10.1039/d0sc06162j.
4
Spliceostatins and Derivatives: Chemical Syntheses and Biological Properties of Potent Splicing Inhibitors.剪接体抑制剂及其衍生物：强效剪接抑制剂的化学合成与生物学特性。
J Nat Prod. 2021 May 28;84(5):1681-1706. doi: 10.1021/acs.jnatprod.1c00100. Epub 2021 May 11.
5
Synthesis of Resolvin E1 and Its Conformationally Restricted Cyclopropane Congeners with Potent Anti-Inflammatory Effect.具有强效抗炎作用的消退素E1及其构象受限环丙烷类似物的合成。
ACS Med Chem Lett. 2021 Jan 21;12(2):256-261. doi: 10.1021/acsmedchemlett.0c00639. eCollection 2021 Feb 11.
6
Crystal structure of (-)-(5,7,8,9,10)-8-methyl-7-[(5)-3-methyl-2-oxooxolan-3-en-5-yl]-1-aza-6-oxatri-cyclo-[8.3.0.0]tridecan-13-one monohydrate.（-）-（5,7,8,9,10）-8-甲基-7- [（5）-3-甲基-2-氧代氧杂环戊-3-烯-5-基] -1-氮杂-6-氧杂三环-[8.3.0.0]十三烷-13-酮一水合物的晶体结构
Acta Crystallogr E Crystallogr Commun. 2018 Mar 27;74(Pt 4):555-558. doi: 10.1107/S2056989018004425. eCollection 2018 Apr 1.
7
A General Asymmetric Synthesis of (R)-Matsutakeol and Flavored Analogs.(R)-松茸醇及其风味类似物的通用不对称合成
Molecules. 2017 Feb 27;22(3):364. doi: 10.3390/molecules22030364.
8
Gold-Catalyzed Vinyl Ether Hydroalkynylation: An Alternative Pathway for the Gold-Catalyzed Intermolecular Reaction of Alkenes and Alkynes.金催化乙烯基醚氢炔基化反应：烯烃和炔烃的金催化分子间反应的另一种途径。
Org Lett. 2016 Dec 16;18(24):6336-6339. doi: 10.1021/acs.orglett.6b03228. Epub 2016 Nov 29.
9
Efficient Access to Multifunctional Trifluoromethyl Alcohols through Base-Free Catalytic Asymmetric C-C Bond Formation with Terminal Ynamides.通过与末端烯酰胺进行无碱催化不对称C-C键形成高效合成多功能三氟甲基醇
Angew Chem Int Ed Engl. 2016 Feb 18;55(8):2929-33. doi: 10.1002/anie.201510910. Epub 2016 Jan 25.
10
Total Synthesis of Chiral Falcarindiol Analogues Using BINOL-Promoted Alkyne Addition to Aldehydes.使用联萘酚促进的炔烃加成到醛的方法对手性法卡林二醇类似物进行全合成。
Molecules. 2016 Jan 19;21(1):E112. doi: 10.3390/molecules21010112.
本文引用的文献
1
Catalytic Enantioselective Reduction of Ketones by a Chiral Gallium Complex and Catecholborane.手性镓配合物与儿茶酚硼烷催化酮的对映选择性还原反应
Angew Chem Int Ed Engl. 1999 Feb 1;38(3):335-336. doi: 10.1002/(SICI)1521-3773(19990201)38:3<335::AID-ANIE335>3.0.CO;2-T.
2
The Enantioselective Addition of Alkyne Nucleophiles to Carbonyl Groups.炔烃亲核试剂对羰基的对映选择性加成
Adv Synth Catal. 2009 May;351(7-8). doi: 10.1002/adsc.200800776.
3
Transition-metal-catalyzed synthesis of aspergillide B: an alkyne addition strategy.过渡金属催化合成aspergillide B：炔烃加成策略。
Org Lett. 2012 Mar 2;14(5):1322-5. doi: 10.1021/ol300200m. Epub 2012 Feb 22.
4
Camphor-based Schiff base ligand SBAIB: an enantioselective catalyst for addition of phenylacetylene to aldehydes.基于樟脑的席夫碱配体 SBAIB：一种对醛与苯乙炔加成反应具有对映选择性的催化剂。
Org Biomol Chem. 2012 Feb 28;10(8):1625-38. doi: 10.1039/c1ob06683h. Epub 2012 Jan 12.
5
Thionium ion initiated medium-sized ring formation: the total synthesis of asteriscunolide D.锍离子引发中等环形成：星绒菊内酯 D 的全合成。
J Am Chem Soc. 2012 Jan 25;134(3):1474-7. doi: 10.1021/ja210986f. Epub 2012 Jan 10.
6
From highly enantioselective catalytic reaction of 1,3-diynes with aldehydes to facile asymmetric synthesis of polycyclic compounds.从 1,3-二炔与醛的高对映选择性催化反应到多环化合物的简便不对称合成。
J Am Chem Soc. 2011 Aug 3;133(30):11780-94. doi: 10.1021/ja204289q. Epub 2011 Jul 11.
7
Asymmetric alkynylation of aldehydes with propiolates without high reagent loading and any additives.醛与丙炔酸酯在无高试剂负载和任何添加剂的情况下不对称炔丙基化。
Org Biomol Chem. 2011 Jun 21;9(12):4425-8. doi: 10.1039/c1ob05489a. Epub 2011 May 6.
8
Enantioselective ProPhenol-catalyzed addition of 1,3-diynes to aldehydes to generate synthetically versatile building blocks and diyne natural products.对映选择性 ProPhenol 催化 1,3-二炔与醛的加成反应，生成具有综合多功能的构建块和二炔天然产物。
J Am Chem Soc. 2010 Apr 14;132(14):5186-92. doi: 10.1021/ja910656b.
9
3,3'-Anisyl-substituted BINOL, H(4)BINOL, and H(8)BINOL ligands: asymmetric synthesis of diverse propargylic alcohols and their ring-closing metathesis to chiral cycloalkenes.3,3'-二甲氧基联苯、H(4)BINOL 和 H(8)BINOL 配体：各种丙炔醇的不对称合成及其环化复分解反应生成手性环烯烃。
J Org Chem. 2009 Nov 20;74(22):8681-9. doi: 10.1021/jo9018446.
10
De novo asymmetric synthesis of cladospolide B-D: structural reassignment of cladospolide D via the synthesis of its enantiomer.从头不对称合成 cladospolide B-D：通过 cladospolide D 的对映异构体合成对其结构进行重新指定。
Org Lett. 2009 Mar 5;11(5):1107-10. doi: 10.1021/ol9000119.
Zotero 插件