通过烃氧化进行大环内酯化反应。
Macrolactonization via hydrocarbon oxidation.
作者信息
Fraunhoffer Kenneth J, Narayanasamy Prabagaran, Sirois Lauren E, White M Christina
机构信息
Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, USA.
出版信息
J Am Chem Soc. 2006 Jul 19;128(28):9032-3. doi: 10.1021/ja063096r.
Abstract
A novel Pd/sulfoxide-catalyzed macrolactonization reaction of linear omega-alkenoic acids is reported that proceeds via serial ligand-catalyzed allylic C-H oxidation. The scope of this macrolactonization appears to be very broad. Aryl, alkyl, and (Z)-alpha,beta-unsaturated acids are all competent nucleophiles for this reaction, with the latter undergoing macrolactonization with no olefin isomerization. High functional group compatibility is observed that includes biologically and medicinally relevant functionality such as ortho-substituted salicylate esters, bis(indoyl)maleimides, and peptides. Evidence is provided to support the hypothesis that macrolactonization proceeds via inner-sphere functionalization from a templated pi-allylPd carboxylate intermediate.
摘要
报道了一种新型的钯/亚砜催化的线性ω-链烯酸大环内酯化反应，该反应通过一系列配体催化的烯丙基C-H氧化进行。这种大环内酯化反应的适用范围似乎非常广泛。芳基、烷基和（Z）-α，β-不饱和酸都是该反应的有效亲核试剂，后者进行大环内酯化反应时没有烯烃异构化。观察到该反应具有高官能团兼容性，包括具有生物学和医学相关性的官能团，如邻位取代的水杨酸酯、双（吲哚基）马来酰亚胺和肽。有证据支持大环内酯化反应通过模板化的π-烯丙基钯羧酸盐中间体的内球官能化进行的假设。
相似文献
1
Macrolactonization via hydrocarbon oxidation.通过烃氧化进行大环内酯化反应。
J Am Chem Soc. 2006 Jul 19;128(28):9032-3. doi: 10.1021/ja063096r.
2
Sequential hydrocarbon functionalization: allylic C-H oxidation/vinylic C-H arylation.顺序烃官能团化：烯丙基C-H氧化/乙烯基C-H芳基化。
J Am Chem Soc. 2006 Nov 29;128(47):15076-7. doi: 10.1021/ja066563d.
3
Transition Metal-Catalyzed Regioselective Direct C-H Amidation: Interplay between Inner- and Outer-Sphere Pathways for Nitrene Cross-Coupling Reactions.过渡金属催化的区域选择性直接 C-H 酰胺化：氮宾交叉偶联反应中内界和外界途径的相互作用。
Acc Chem Res. 2022 Aug 2;55(15):2123-2137. doi: 10.1021/acs.accounts.2c00283. Epub 2022 Jul 19.
4
Terminal olefins to chromans, isochromans, and pyrans via allylic C-H oxidation.通过烯丙基C-H氧化将末端烯烃转化为色满、异色满和吡喃。
J Am Chem Soc. 2014 Aug 6;136(31):10834-7. doi: 10.1021/ja503322e. Epub 2014 Jul 16.
5
Chiral Amines via Enantioselective π-Allyliridium-,-Benzoate-Catalyzed Allylic Alkylation: Student Training via Industrial-Academic Collaboration.手性胺的对映选择性π-烯丙基铱-，-苯甲酸酯催化的烯丙基烷基化：通过产学合作进行学生培训。
Acc Chem Res. 2022 Aug 2;55(15):2138-2147. doi: 10.1021/acs.accounts.2c00302. Epub 2022 Jul 13.
6
N-Boc amines to oxazolidinones via Pd(II)/bis-sulfoxide/Brønsted acid co-catalyzed allylic C-H oxidation.通过钯（II）/双亚砜/布朗斯特酸共催化的烯丙基C-H氧化反应将N-叔丁氧羰基胺转化为恶唑烷酮。
J Am Chem Soc. 2014 Aug 6;136(31):11176-81. doi: 10.1021/ja506036q. Epub 2014 Jul 24.
7
Serial ligand catalysis: a highly selective allylic C-H oxidation.串联配体催化：一种高度选择性的烯丙基C-H氧化反应
J Am Chem Soc. 2005 May 18;127(19):6970-1. doi: 10.1021/ja0500198.
8
General allylic C-H alkylation with tertiary nucleophiles.使用叔亲核试剂进行的一般烯丙基C-H烷基化反应。
J Am Chem Soc. 2014 Apr 16;136(15):5750-4. doi: 10.1021/ja500726e. Epub 2014 Apr 2.
9
Catalytic intermolecular allylic C-H alkylation.催化分子间烯丙基C-H烷基化反应
J Am Chem Soc. 2008 Oct 29;130(43):14090-1. doi: 10.1021/ja806867p. Epub 2008 Oct 3.
10
Mg(OMe) promoted allylic isomerization of γ-hydroxy-α,β-alkenoic esters to synthesize γ-ketone esters.甲醇镁促进γ-羟基-α,β-烯酸酯的烯丙基异构化反应以合成γ-酮酯。
Org Biomol Chem. 2017 Mar 8;15(10):2185-2190. doi: 10.1039/c7ob00131b.
引用本文的文献
1
Stereoselective Synthesis of Chiral -Symmetric 1,3- and 1,5-Bis-Sulfoxides Guided by the Horeau Principle: Understanding the Influence of the Carbon Chain Nature in Its Ability for Metal Coordination.霍劳原理指导下的手性对称1,3-和1,5-双亚砜的立体选择性合成：理解碳链性质对其金属配位能力的影响
J Org Chem. 2024 Oct 18;89(20):15048-15061. doi: 10.1021/acs.joc.4c01729. Epub 2024 Oct 2.
2
Synthesis of Benzodioxepinones and Benzoxazepinones via Tandem Oxidation and Iodolactonization of 2-/-tethered Alkenyl Benzaldehyde Mediated by CuI/TBHP.通过CuI/TBHP介导的2-/-连接的烯基苯甲醛的串联氧化和碘内酯化反应合成苯并二氧杂环庚酮和苯并恶嗪酮。
ACS Omega. 2024 Mar 12;9(12):14217-14232. doi: 10.1021/acsomega.3c09878. eCollection 2024 Mar 26.
3
Pd(II)-Catalyzed Synthesis of Bicyclo[3.2.1] Lactones Tandem Intramolecular β-C(sp)-H Olefination and Lactonization of Free Carboxylic Acids.Pd(II)催化的双环[3.2.1]内酯的串联分子内β-C(sp3)-H 烯烃化和游离羧酸的内酯化反应。
J Am Chem Soc. 2022 Jul 13;144(27):11955-11960. doi: 10.1021/jacs.2c04195. Epub 2022 Jun 28.
4
Regio- and enantioselective remote hydroarylation using a ligand-relay strategy.区域和对映选择性远程氢芳基化反应的配体接力策略。
Nat Commun. 2022 May 5;13(1):2471. doi: 10.1038/s41467-022-30006-2.
5
Pd-catalysed C-H functionalisation of free carboxylic acids.钯催化的游离羧酸的C-H官能化反应。
Chem Sci. 2022 Jan 10;13(9):2551-2573. doi: 10.1039/d1sc05392b. eCollection 2022 Mar 2.
6
Ligand-Enabled γ-C(sp )-H Olefination of Free Carboxylic Acids.配体促进的游离羧酸的γ-C(sp )-H 烯烃化反应。
Angew Chem Int Ed Engl. 2020 Jul 27;59(31):12848-12852. doi: 10.1002/anie.202002362. Epub 2020 May 18.
7
Metal-Free C-H Functionalization of Allenamides: An Access to Branched Allylic Esters.烯丙酰胺的无金属C-H官能团化：一种合成支链烯丙基酯的方法。
ACS Omega. 2019 Sep 9;4(12):15312-15322. doi: 10.1021/acsomega.9b02712. eCollection 2019 Sep 17.
8
Operando Spectroscopic and Kinetic Characterization of Aerobic Allylic C-H Acetoxylation Catalyzed by Pd(OAc)/4,5-Diazafluoren-9-one.钯（Ⅱ）/4,5-二氮芴-9-酮催化的有氧烯丙位 C-H 乙酰化的原位光谱学和动力学表征。
J Am Chem Soc. 2019 Jul 3;141(26):10462-10474. doi: 10.1021/jacs.9b04699. Epub 2019 Jun 25.
9
Aerobic Acyloxylation of Allylic C-H Bonds Initiated by a Pd Precatalyst with 4,5-Diazafluoren-9-one as an Ancillary Ligand.以4,5-二氮杂芴-9-酮为辅助配体的钯预催化剂引发的烯丙基C-H键的有氧酰氧基化反应。
ChemSusChem. 2019 Jul 5;12(13):3003-3007. doi: 10.1002/cssc.201900727. Epub 2019 Jun 5.
10
The Therapeutic Potential of Migrastatin-Core Analogs for the Treatment of Metastatic Cancer.米格拉他汀核心类似物在治疗转移性癌症方面的治疗潜力。
Molecules. 2017 Feb 9;22(2):198. doi: 10.3390/molecules22020198.
本文引用的文献
1
Macrolactonizations in the total synthesis of natural products.天然产物全合成中的大环内酯化反应。
Chem Rev. 2006 Mar;106(3):911-39. doi: 10.1021/cr0301402.
2
Catalytic Ni/Cr-mediated macrocyclization without use of high-dilution techniques.无需使用高稀释技术的催化镍/铬介导的大环化反应。
J Am Chem Soc. 2005 Nov 9;127(44):15382-3. doi: 10.1021/ja055966v.
3
Design, synthesis, and biological evaluation of HSP90 inhibitors based on conformational analysis of radicicol and its analogues.基于根赤壳菌素及其类似物构象分析的HSP90抑制剂的设计、合成及生物学评价
J Am Chem Soc. 2005 May 18;127(19):6999-7004. doi: 10.1021/ja043101w.
4
Serial ligand catalysis: a highly selective allylic C-H oxidation.串联配体催化：一种高度选择性的烯丙基C-H氧化反应
J Am Chem Soc. 2005 May 18;127(19):6970-1. doi: 10.1021/ja0500198.
5
Synthesis of functionalized salicylate esters and amides by photochemical acylation.通过光化学酰化反应合成功能化水杨酸酯和酰胺。
Angew Chem Int Ed Engl. 2005 Mar 4;44(11):1696-9. doi: 10.1002/anie.200462577.
6
Hydrocarbon oxidation vs C-C bond-forming approaches for efficient syntheses of oxygenated molecules.用于高效合成氧化分子的碳氢化合物氧化与碳-碳键形成方法的比较
Org Lett. 2005 Jan 20;7(2):223-6. doi: 10.1021/ol047800p.
7
Chemistry and biology of cyclic depsipeptides of medicinal and biological interest.具有医学和生物学意义的环缩肽的化学与生物学
Curr Med Chem. 2004 May;11(10):1309-32. doi: 10.2174/0929867043365224.
8
A sulfoxide-promoted, catalytic method for the regioselective synthesis of allylic acetates from monosubstituted olefins via C-H oxidation.一种由亚砜促进的、通过C-H氧化从单取代烯烃区域选择性合成烯丙基乙酸酯的催化方法。
J Am Chem Soc. 2004 Feb 11;126(5):1346-7. doi: 10.1021/ja039107n.
9
Chemistry and biology of salicylihalamide a and related compounds.水杨酰胺A及相关化合物的化学与生物学
Chem Rev. 2003 Nov;103(11):4283-306. doi: 10.1021/cr030035s.
10
Synthesis of the macrocyclic core of laulimalide.劳利霉素大环核心的合成。
Org Lett. 2001 Jan 25;3(2):213-6. doi: 10.1021/ol000342+.
Zotero 插件