过渡金属催化的天然产物中 C(sp )-H 键的选择性功能化。
Transition-Metal-Catalyzed Selective Functionalization of C(sp )-H Bonds in Natural Products.
机构信息
Department of Chemistry, 718 Latimer Hall, University of California, Berkely, Berkeley, CA, 94708, USA.
出版信息
Angew Chem Int Ed Engl. 2018 Apr 9;57(16):4234-4241. doi: 10.1002/anie.201710330. Epub 2018 Feb 14.
Abstract
Direct functionalization of natural products is important for studying the structure-activity and structure-property relationships of these molecules. Recent advances in the transition-metal-catalyzed functionalization of C(sp )-H bonds, the most abundant yet inert bonds in natural products, have allowed natural product derivatives to be created selectively. Strategies to achieve such transformation are reviewed.
摘要
直接对天然产物进行功能化对于研究这些分子的结构-活性和结构-性质关系非常重要。最近在过渡金属催化的 C(sp )-H 键功能化方面的进展，使得天然产物中最丰富但惰性的键能够被选择性地转化，从而可以生成天然产物衍生物。本文综述了实现这种转化的策略。
相似文献
1
Transition-Metal-Catalyzed Selective Functionalization of C(sp )-H Bonds in Natural Products.过渡金属催化的天然产物中 C(sp )-H 键的选择性功能化。
Angew Chem Int Ed Engl. 2018 Apr 9;57(16):4234-4241. doi: 10.1002/anie.201710330. Epub 2018 Feb 14.
2
Bidentate, monoanionic auxiliary-directed functionalization of carbon-hydrogen bonds.双齿单阴离子辅助导向的碳氢键官能团化
Acc Chem Res. 2015 Apr 21;48(4):1053-64. doi: 10.1021/ar5004626. Epub 2015 Mar 10.
3
Efficient synthesis strategies by application of transition metal-catalyzed carbene/nitrene insertions into C-H bonds.通过应用过渡金属催化的卡宾/氮宾插入 C-H 键的高效合成策略。
Nat Prod Rep. 2014 Apr;31(4):449-55. doi: 10.1039/c3np70084d. Epub 2014 Mar 4.
4
Recent advances in theoretical studies on transition-metal-catalyzed regioselective C-H functionalization of indoles.吲哚的过渡金属催化区域选择性 C-H 功能化的理论研究进展。
J Mol Model. 2022 Aug 22;28(9):267. doi: 10.1007/s00894-022-05265-x.
5
Development of Transition-Metal-Catalysed Cross-Coupling Reactions through Ammonium C-N Bond Cleavage.通过铵 C-N 键断裂开发过渡金属催化的交叉偶联反应。
Chem Pharm Bull (Tokyo). 2020;68(8):683-693. doi: 10.1248/cpb.c20-00196.
6
Recent advances in transition-metal-catalyzed carbene insertion to C-H bonds.过渡金属催化卡宾插入 C-H 键的最新进展。
Chem Soc Rev. 2022 Apr 4;51(7):2759-2852. doi: 10.1039/d1cs00895a.
7
Toolbox for Distal C-H Bond Functionalizations in Organic Molecules.有机分子中远端碳氢键官能团化的工具箱
Chem Rev. 2022 Mar 23;122(6):5682-5841. doi: 10.1021/acs.chemrev.1c00220. Epub 2021 Oct 18.
8
Recent Developments in Transition-Metal Catalyzed Direct C-H Alkenylation, Alkylation, and Alkynylation of Azoles.过渡金属催化唑类化合物的 C-H 直接烯基化、烷基化和炔基化反应的最新进展。
Molecules. 2020 Oct 27;25(21):4970. doi: 10.3390/molecules25214970.
9
Transition-Metal-Catalyzed, Coordination-Assisted Functionalization of Nonactivated C(sp)-H Bonds.过渡金属催化的非活化 C(sp3)-H 键的配位辅助功能化。
Chem Rev. 2021 Dec 22;121(24):14957-15074. doi: 10.1021/acs.chemrev.1c00519. Epub 2021 Oct 29.
10
Recent advances in the transition metal-catalyzed twofold oxidative C-H bond activation strategy for C-C and C-N bond formation.过渡金属催化的双重氧化 C-H 键活化策略在 C-C 和 C-N 键形成中的最新进展。
Chem Soc Rev. 2011 Oct;40(10):5068-83. doi: 10.1039/c1cs15082k. Epub 2011 Jun 6.
引用本文的文献
1
Iron-Catalyzed Carbonylation Reactions with Carbon Monoxide.铁催化的与一氧化碳的羰基化反应。
Angew Chem Int Ed Engl. 2025 Sep 1;64(36):e202512346. doi: 10.1002/anie.202512346. Epub 2025 Aug 10.
2
Asymmetric total synthesis of benzenoid cephalotane-type diterpenoids through a cascade C(sp) & C(sp)-H activation.通过串联C(sp)和C(sp)-H活化实现苯并环戊烷型二萜类化合物的不对称全合成。
Nat Commun. 2025 May 20;16(1):4674. doi: 10.1038/s41467-025-59816-w.
3
A Chemoenzymatic Cascade for the Formal Enantioselective Hydroxylation and Amination of Benzylic C-H Bonds.一种用于苄基C-H键的形式对映选择性羟基化和胺化的化学酶级联反应。
ACS Catal. 2024 Nov 12;14(23):17405-17412. doi: 10.1021/acscatal.4c03161. eCollection 2024 Dec 6.
4
Ruthenaelectro-catalyzed C-H phosphorylation: to position-selectivity switch.钌电催化的C-H磷酸化：实现位置选择性切换。
Chem Sci. 2024 Nov 29;16(2):824-833. doi: 10.1039/d4sc06219a. eCollection 2025 Jan 2.
5
Repurposing a supramolecular iridium catalyst secondary Zn⋯O[double bond, length as m-dash]C weak interactions between the ligand and substrate leads to -selective C(sp)-H borylation of benzamides with unusual kinetics.重新利用一种超分子铱催化剂，配体与底物之间的二级Zn⋯O[双键，长度为中划线]C弱相互作用导致苯甲酰胺的选择性C(sp)-H硼化反应具有异常的动力学。
Chem Sci. 2024 Jun 14;15(30):11794-11806. doi: 10.1039/d4sc01515k. eCollection 2024 Jul 31.
6
Studies towards the Enantioselective Synthesis of Cryptowolinol via Pd-Catalyzed C(sp)-H Arylation/Parallel Kinetic Resolution.通过钯催化的C(sp)-H芳基化/平行动力学拆分对隐沃林醇进行对映选择性合成的研究。
Org Lett. 2024 Apr 19;26(15):2923-2927. doi: 10.1021/acs.orglett.4c00386. Epub 2024 Apr 3.
7
Regioselective Hydroxylation of Unsymmetrical Ketones Using Cu, HO, and Imine Directing Groups via Formation of an Electrophilic Cupric Hydroperoxide Core.通过形成亲电过氧化铜核心，利用铜、羟基和亚胺导向基团对不对称酮进行区域选择性羟基化反应。
J Org Chem. 2024 Feb 16;89(4):2622-2636. doi: 10.1021/acs.joc.3c02647. Epub 2024 Feb 7.
8
Molecular Editing of Pyrroles via a Skeletal Recasting Strategy.通过骨架重塑策略对吡咯进行分子编辑
ACS Cent Sci. 2023 Aug 15;9(9):1758-1767. doi: 10.1021/acscentsci.3c00812. eCollection 2023 Sep 27.
9
Strategic application of C-H oxidation in natural product total synthesis.C-H氧化在天然产物全合成中的策略性应用。
Nat Rev Chem. 2023 Nov;7(11):783-799. doi: 10.1038/s41570-023-00534-6. Epub 2023 Sep 20.
10
Recent Advances in C-H Functionalisation through Indirect Hydrogen Atom Transfer.通过间接氢原子转移实现C-H官能化的最新进展
Molecules. 2023 Aug 18;28(16):6127. doi: 10.3390/molecules28166127.
本文引用的文献
1
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.
2
Late Stage Azidation of Complex Molecules.复杂分子的后期叠氮化
ACS Cent Sci. 2016 Oct 26;2(10):715-724. doi: 10.1021/acscentsci.6b00214. Epub 2016 Oct 7.
3
Undirected, Homogeneous C-H Bond Functionalization: Challenges and Opportunities.无导向、均相C-H键官能团化：挑战与机遇
ACS Cent Sci. 2016 May 25;2(5):281-92. doi: 10.1021/acscentsci.6b00032. Epub 2016 May 2.
4
Natural Products as Sources of New Drugs from 1981 to 2014.1981年至2014年作为新药来源的天然产物
J Nat Prod. 2016 Mar 25;79(3):629-61. doi: 10.1021/acs.jnatprod.5b01055. Epub 2016 Feb 7.
5
Evolution of C-H Bond Functionalization from Methane to Methodology.从甲烷到方法学：C-H键官能团化的演变
J Am Chem Soc. 2016 Jan 13;138(1):2-24. doi: 10.1021/jacs.5b08707. Epub 2015 Dec 15.
6
Scalable C-H Oxidation with Copper: Synthesis of Polyoxypregnanes.铜催化的可扩展C-H氧化反应：多氧孕甾烷的合成。
J Am Chem Soc. 2015 Nov 4;137(43):13776-9. doi: 10.1021/jacs.5b09463. Epub 2015 Oct 21.
7
Diverse sp(3) C-H functionalization through alcohol β-sulfonyloxylation.通过醇的β-砜酰氧基化实现多样的 sp(3) C-H 官能团化。
Nat Chem. 2015 Oct;7(10):829-34. doi: 10.1038/nchem.2326. Epub 2015 Aug 24.
8
Manganese-catalyzed late-stage aliphatic C-H azidation.锰催化的后期脂肪族 C-H 叠氮化反应。
J Am Chem Soc. 2015 Apr 29;137(16):5300-3. doi: 10.1021/jacs.5b01983. Epub 2015 Apr 14.
9
Metal-catalysed azidation of tertiary C-H bonds suitable for late-stage functionalization.适用于后期官能化的叔碳C-H键的金属催化叠氮化反应。
Nature. 2015 Jan 29;517(7536):600-4. doi: 10.1038/nature14127.
10
A convenient photocatalytic fluorination of unactivated C-H bonds.一种方便的未活化 C-H 键光催化氟化方法。
Angew Chem Int Ed Engl. 2014 Apr 25;53(18):4690-3. doi: 10.1002/anie.201400420. Epub 2014 Mar 25.
Zotero 插件