将含烯烃的天然产物进行环丙烷化反应，同时进行结构活性研究。
Cyclopropanations of olefin-containing natural products for simultaneous arming and structure activity studies.
机构信息
Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842-3012, United States.
出版信息
Org Lett. 2012 Mar 16;14(6):1394-7. doi: 10.1021/ol300105q. Epub 2012 Feb 24.
Abstract
Cyclopropanations of alkene-containing natural products that proceed under mild conditions are reported for simultaneous arming and structure-activity relationship studies. An alkynyl diazo ester under Rh(II) catalysis is employed for cyclopropanations of electron-rich olefins while an alkynyl sulfonium ylide is used for electron-poor olefins. This approach enables simultaneous natural product derivatization for SAR studies and arming (i.e., via alkyne attachment) for subsequent conjugation with reporter tags (e.g., biotin, fluorophores, photoaffinity labels) for mechanism of action studies including cellular target identification and proteome profiling experiments.
摘要
报道了在温和条件下进行的含烯烃天然产物的环丙烷化反应，用于同时进行的武器化和构效关系研究。在 Rh(II)催化下，使用炔基重氮酯进行富电子烯烃的环丙烷化反应，而使用炔基硫叶立德进行缺电子烯烃的环丙烷化反应。这种方法能够同时对天然产物进行衍生化以进行 SAR 研究，并进行武器化（即通过炔键连接），以便随后与报告标签（如生物素、荧光团、光亲和标记物）缀合，用于作用机制研究，包括细胞靶标鉴定和蛋白质组分析实验。
相似文献
1
Cyclopropanations of olefin-containing natural products for simultaneous arming and structure activity studies.将含烯烃的天然产物进行环丙烷化反应，同时进行结构活性研究。
Org Lett. 2012 Mar 16;14(6):1394-7. doi: 10.1021/ol300105q. Epub 2012 Feb 24.
2
Simultaneous arming and structure/activity studies of natural products employing O-H insertions: an expedient and versatile strategy for natural products-based chemical genetics.利用O-H插入对天然产物进行同步武装和结构/活性研究：一种基于天然产物的化学遗传学的便捷通用策略。
J Am Chem Soc. 2007 Oct 10;129(40):12222-31. doi: 10.1021/ja0733686. Epub 2007 Sep 19.
3
Simultaneous structure-activity studies and arming of natural products by C-H amination reveal cellular targets of eupalmerin acetate.通过 C-H 胺化对天然产物进行同时的结构-活性研究和武装，揭示了醋酸橙花叔醇的细胞靶标。
Nat Chem. 2013 Jun;5(6):510-7. doi: 10.1038/nchem.1653. Epub 2013 May 19.
4
Enantioselective Cyclobutenylation of Olefins Using -Sulfonyl-1,2,3-Triazoles as Vicinal Dicarbene Equivalents.手性磺酰基 1,2,3-三唑作为偕二磺酰亚胺等价物对烯烃的立体选择性环丁烯化反应。
Org Lett. 2021 Aug 20;23(16):6530-6535. doi: 10.1021/acs.orglett.1c02331. Epub 2021 Aug 10.
5
Mild arming and derivatization of natural products via an In(OTf)3-catalyzed arene iodination.通过 In(OTf)3 催化的芳基碘化反应实现天然产物的温和衍生化。
Org Lett. 2010 May 7;12(9):2104-7. doi: 10.1021/ol100587j.
6
Hypervalent iodine(III)-mediated cyclopropa(e)nation of alkenes/alkynes under mild conditions.高价碘（III）介导的烯烃/炔烃在温和条件下的环丙烷化反应。
Org Biomol Chem. 2014 Feb 28;12(8):1341-50. doi: 10.1039/c3ob42123f.
7
Diazo reagents with small steric footprints for simultaneous arming/SAR studies of alcohol-containing natural products via O-H insertion.具有小空间位阻的重氮试剂，用于通过 O-H 插入对含醇天然产物进行同时的臂化/SAR 研究。
ACS Chem Biol. 2011 Nov 18;6(11):1175-81. doi: 10.1021/cb2002686. Epub 2011 Sep 28.
8
Iron-catalyzed preparation of trifluoromethyl substituted vinyl- and alkynylcyclopropanes.铁催化制备三氟甲基取代的乙烯基和炔基环丙烷。
Org Lett. 2011 Jun 17;13(12):3080-1. doi: 10.1021/ol200983s. Epub 2011 May 17.
9
1,4-Pentenyne as a five-carbon synthon for efficient and selective syntheses of natural products containing 2,4-dimethyl-1-penten-1,5-ylidene and related moieties by means of Zr-catalyzed carboalumination of alkynes and alkenes.1,4-戊烯炔作为一种五碳合成子，用于通过锆催化的炔烃和烯烃的碳铝化反应高效、选择性地合成含有2,4-二甲基-1-戊烯-1,5-亚基及相关基团的天然产物。
Chemistry. 2008;14(1):311-8. doi: 10.1002/chem.200701512.
10
Radical Monofluoroalkylative Alkynylation of Olefins by a Docking-Migration Strategy.通过对接-迁移策略实现烯烃的自由基单氟烷基炔基化反应。
Angew Chem Int Ed Engl. 2019 Dec 2;58(49):17646-17650. doi: 10.1002/anie.201910514. Epub 2019 Oct 21.
引用本文的文献
1
Synthesis of Vicinal Carbocycles by Intramolecular Nickel-Catalyzed Conjunctive Cross-Electrophile Coupling Reaction.通过分子内镍催化的共轭交叉电偶联反应合成顺式碳环。
Org Lett. 2022 Aug 19;24(32):6093-6098. doi: 10.1021/acs.orglett.2c02481. Epub 2022 Aug 4.
2
Zinc-Mediated Transformation of 1,3-Diols to Cyclopropanes for Late-Stage Modification of Natural Products and Medicinal Agents.锌介导的 1,3-二醇转化为环丙烷用于天然产物和药物的后期修饰。
Org Lett. 2022 Aug 5;24(30):5619-5623. doi: 10.1021/acs.orglett.2c02362. Epub 2022 Jul 22.
3
Applications of Nonenzymatic Catalysts to the Alteration of Natural Products.非酶催化剂在天然产物改性中的应用。
Chem Rev. 2017 Sep 27;117(18):11894-11951. doi: 10.1021/acs.chemrev.7b00022. Epub 2017 Jun 5.
4
Radicals: Reactive Intermediates with Translational Potential.自由基：具有转化潜能的反应中间体。
J Am Chem Soc. 2016 Oct 5;138(39):12692-12714. doi: 10.1021/jacs.6b08856. Epub 2016 Sep 26.
5
Chemo- and site-selective derivatizations of natural products enabling biological studies.通过化学和部位选择性衍生化天然产物，以进行生物学研究。
Nat Prod Rep. 2014 Mar;31(3):318-34. doi: 10.1039/c3np70087a.
6
Bioconjugation by native chemical tagging of C-H bonds.通过C-H键的天然化学标记进行生物共轭。
J Am Chem Soc. 2013 Sep 4;135(35):12994-7. doi: 10.1021/ja407739y. Epub 2013 Aug 22.
7
Simultaneous structure-activity studies and arming of natural products by C-H amination reveal cellular targets of eupalmerin acetate.通过 C-H 胺化对天然产物进行同时的结构-活性研究和武装，揭示了醋酸橙花叔醇的细胞靶标。
Nat Chem. 2013 Jun;5(6):510-7. doi: 10.1038/nchem.1653. Epub 2013 May 19.
8
Chemoselective hydroxyl group transformation: an elusive target.化学选择性羟基转化：一个难以实现的目标。
Mol Biosyst. 2012 Oct;8(10):2484-93. doi: 10.1039/c2mb25122a.
本文引用的文献
1
Diazo reagents with small steric footprints for simultaneous arming/SAR studies of alcohol-containing natural products via O-H insertion.具有小空间位阻的重氮试剂，用于通过 O-H 插入对含醇天然产物进行同时的臂化/SAR 研究。
ACS Chem Biol. 2011 Nov 18;6(11):1175-81. doi: 10.1021/cb2002686. Epub 2011 Sep 28.
2
Silver triflate-catalyzed cyclopropenation of internal alkynes with donor-/acceptor-substituted diazo compounds.三氟甲磺酸银催化内炔烃与给体/受体取代的重氮化合物的环丙烷化反应。
Org Lett. 2011 Aug 5;13(15):3984-7. doi: 10.1021/ol201503j. Epub 2011 Jun 27.
3
Scope and limitations of cyclopropanations with sulfur ylides.硫叶立德环丙烷化的范围和局限性。
J Am Chem Soc. 2010 Dec 22;132(50):17894-900. doi: 10.1021/ja1084749. Epub 2010 Nov 29.
4
Highly enantioselective Rh2(S-DOSP)4-catalyzed cyclopropenation of alkynes with styryldiazoacetates.高对映选择性 Rh2(S-DOSP)4 催化的炔烃与苯乙烯基重氮乙酸酯的环丙烷化反应。
J Am Chem Soc. 2010 Dec 8;132(48):17211-5. doi: 10.1021/ja106509b. Epub 2010 Nov 16.
5
Silver-catalyzed late-stage fluorination.银催化的晚期氟化反应。
J Am Chem Soc. 2010 Sep 1;132(34):12150-4. doi: 10.1021/ja105834t.
6
Natural products as chemical probes.天然产物作为化学探针。
ACS Chem Biol. 2010 Jul 16;5(7):639-53. doi: 10.1021/cb100105c.
7
Mild arming and derivatization of natural products via an In(OTf)3-catalyzed arene iodination.通过 In(OTf)3 催化的芳基碘化反应实现天然产物的温和衍生化。
Org Lett. 2010 May 7;12(9):2104-7. doi: 10.1021/ol100587j.
8
Privileged scaffolds for library design and drug discovery.优先支架用于文库设计和药物发现。
Curr Opin Chem Biol. 2010 Jun;14(3):347-61. doi: 10.1016/j.cbpa.2010.02.018. Epub 2010 Mar 18.
9
An approach to the site-selective diversification of apoptolidin A with peptide-based catalysts.一种使用基于肽的催化剂对凋亡素A进行位点选择性多样化修饰的方法。
J Nat Prod. 2009 Oct;72(10):1864-9. doi: 10.1021/np9004932.
10
Natural products in drug discovery.药物研发中的天然产物
Drug Discov Today. 2008 Oct;13(19-20):894-901. doi: 10.1016/j.drudis.2008.07.004. Epub 2008 Aug 22.
Zotero 插件