可见光光氧化还原催化羧酸衍生物的定向 γ-C(sp3)-H 烷基化反应。
Directed γ-C(sp)-H Alkylation of Carboxylic Acid Derivatives through Visible Light Photoredox Catalysis.
机构信息
Department of Chemistry, Columbia University , New York, New York 10027, United States.
Department of Chemistry, Colorado State University , Fort Collins, Colorado 80523, United States.
出版信息
J Am Chem Soc. 2017 Oct 25;139(42):14897-14900. doi: 10.1021/jacs.7b09306. Epub 2017 Oct 12.
Abstract
Visible light photoredox catalysis enables direct γ- C(sp)-H alkylation of saturated aliphatic carbonyl compounds. Electron-deficient alkenes are used as the coupling partners in this reaction. Distinguished site selectivity is controlled by the predominant 1,5-hydrogen atom transfer of an amidyl radical generated in situ.
摘要
可见光阴极催化实现了饱和脂肪族羰基化合物的直接γ-C(sp3)-H 烷基化。在该反应中，缺电子烯烃被用作偶联试剂。通过原位生成的酰基自由基的主要 1,5-氢原子转移来控制显著的位置选择性。
相似文献
1
Directed γ-C(sp)-H Alkylation of Carboxylic Acid Derivatives through Visible Light Photoredox Catalysis.可见光光氧化还原催化羧酸衍生物的定向 γ-C(sp3)-H 烷基化反应。
J Am Chem Soc. 2017 Oct 25;139(42):14897-14900. doi: 10.1021/jacs.7b09306. Epub 2017 Oct 12.
2
Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer.质子耦合电子转移实现的远程C-H键催化烷基化反应。
Nature. 2016 Nov 10;539(7628):268-271. doi: 10.1038/nature19811. Epub 2016 Oct 12.
3
Photoredox-Catalyzed Site-Selective α-C(sp )-H Alkylation of Primary Amine Derivatives.光氧化还原催化的一级胺衍生物的α-C(sp3)-H 位点选择性烷基化反应。
Angew Chem Int Ed Engl. 2019 Mar 18;58(12):4002-4006. doi: 10.1002/anie.201812227. Epub 2019 Feb 15.
4
Visible-Light Photoredox-Catalyzed Giese Reaction: Decarboxylative Addition of Amino Acid Derived α-Amino Radicals to Electron-Deficient Olefins.可见光光氧化还原催化的吉泽反应：氨基酸衍生的α-氨基自由基向缺电子烯烃的脱羧加成反应。
Chemistry. 2016 Sep 12;22(38):13464-8. doi: 10.1002/chem.201602257. Epub 2016 Jun 20.
5
Pyrimidopteridine-catalyzed Photo-mediated Hydroacetoxylation.嘧啶并嘧啶酮催化的光介导的羟乙酰化反应。
Chemistry. 2022 Oct 12;28(57):e202201761. doi: 10.1002/chem.202201761. Epub 2022 Aug 24.
6
In situ EPR studies of reaction pathways in Titania photocatalyst-promoted alkylation of alkenes.二氧化钛光催化剂促进烯烃烷基化反应途径的原位电子顺磁共振研究
Molecules. 2015 Mar 3;20(3):4055-70. doi: 10.3390/molecules20034055.
7
A general deoxygenation approach for synthesis of ketones from aromatic carboxylic acids and alkenes.一种通用的脱氧方法，用于从芳香羧酸和烯烃合成酮。
Nat Commun. 2018 Aug 29;9(1):3517. doi: 10.1038/s41467-018-06019-1.
8
Selective reduction of carboxylic acids to aldehydes with hydrosilane via photoredox catalysis.通过光氧化还原催化，利用硅烷将羧酸选择性还原为醛。
Chem Commun (Camb). 2017 Sep 12;53(73):10228-10231. doi: 10.1039/c7cc05570f.
9
Transition-metal-free visible-light photoredox catalysis at room-temperature for decarboxylative fluorination of aliphatic carboxylic acids by organic dyes.室温下无过渡金属的可见光光氧化还原催化：有机染料用于脂肪族羧酸的脱羧氟化反应
Chem Commun (Camb). 2015 Jul 28;51(59):11864-7. doi: 10.1039/c5cc04527d.
10
Organophotoredox-Catalyzed Three-Component Coupling of Heteroatom Nucleophiles, Alkenes, and Aliphatic Redox Active Esters.有机光氧化还原催化的杂原子亲核试剂、烯烃和脂肪族氧化还原活性酯的三组分偶联反应。
Org Lett. 2021 Mar 5;23(5):1798-1803. doi: 10.1021/acs.orglett.1c00211. Epub 2021 Feb 11.
引用本文的文献
1
Visible-light-driven net-1,2-hydrogen atom transfer of amidyl radicals to access β-amido ketone derivatives.可见光驱动的酰胺基自由基的1,2-氢原子净转移以获得β-酰胺基酮衍生物。
Chem Sci. 2024 Dec 3;16(2):962-969. doi: 10.1039/d4sc04997g. eCollection 2025 Jan 2.
2
Stereoselective and site-divergent synthesis of C-glycosides.C-糖苷的立体选择性和位点发散性合成。
Nat Chem. 2024 Dec;16(12):2054-2065. doi: 10.1038/s41557-024-01629-3. Epub 2024 Sep 13.
3
Sulfonamide-directed site-selective functionalization of unactivated C(sp)-H enabled by photocatalytic sequential electron/proton transfer.光催化顺序电子/质子转移实现未活化C(sp)-H的磺胺导向位点选择性官能化
Nat Commun. 2024 Jun 14;15(1):5087. doi: 10.1038/s41467-024-49337-3.
4
Versatile Copper-Catalyzed γ-C(sp)-H Lactonization of Aliphatic Acids.通用的铜催化脂肪酸的γ-C(sp)-H内酯化反应
J Am Chem Soc. 2024 Jun 26;146(25):17311-17317. doi: 10.1021/jacs.4c04043. Epub 2024 Jun 12.
5
Transformations of carbohydrate derivatives enabled by photocatalysis and visible light photochemistry.光催化和可见光光化学实现的碳水化合物衍生物的转化
Chem Sci. 2024 Jan 2;15(4):1204-1236. doi: 10.1039/d3sc05400d. eCollection 2024 Jan 24.
6
Exploiting photoredox catalysis for carbohydrate modification through C-H and C-C bond activation.通过碳氢键和碳碳键活化利用光氧化还原催化进行碳水化合物修饰。
Nat Rev Chem. 2022 Nov;6(11):782-805. doi: 10.1038/s41570-022-00422-5. Epub 2022 Sep 21.
7
Modular synthesis of unsaturated aza-heterocycles via copper catalyzed multicomponent cascade reaction.通过铜催化多组分串联反应实现不饱和氮杂环的模块化合成。
iScience. 2023 Feb 9;26(3):106137. doi: 10.1016/j.isci.2023.106137. eCollection 2023 Mar 17.
8
General and Selective Metal-Free Radical -C-H Borylation of Aliphatic Amines.脂肪族胺的通用和选择性无金属自由基-C-H硼化反应
Chem. 2022 Nov;8(11):3096-3108. doi: 10.1016/j.chempr.2022.07.022. Epub 2022 Aug 22.
9
Multiple remote C(sp)-H functionalizations of aliphatic ketones bimetallic Cu-Pd catalyzed successive dehydrogenation.脂肪族酮的多远程C(sp)-H官能团化：双金属铜-钯催化的连续脱氢反应
Chem Sci. 2022 Nov 14;13(46):13843-13850. doi: 10.1039/d2sc05370e. eCollection 2022 Nov 30.
10
Investigations into mechanism and origin of regioselectivity in the metallaphotoredox-catalyzed α-arylation of -alkylbenzamides.金属光氧化还原催化的α-烷基苯甲酰胺α-芳基化区域选择性的机理与起源研究。
Chem Sci. 2022 Aug 19;13(35):10566-10573. doi: 10.1039/d2sc01962k. eCollection 2022 Sep 14.
本文引用的文献
1
Palladium-Catalyzed Transformations of Alkyl C-H Bonds.钯催化的烷基碳氢键转化反应
Chem Rev. 2017 Jul 12;117(13):8754-8786. doi: 10.1021/acs.chemrev.6b00622. Epub 2016 Dec 2.
2
Formation of α-chiral centers by asymmetric β-C(sp3)-H arylation, alkenylation, and alkynylation.通过不对称β-C(sp3)-H芳基化、烯基化和炔基化形成α-手性中心。
Science. 2017 Feb 3;355(6324):499-503. doi: 10.1126/science.aal5175.
3
Synthesis of Lactones via C-H Functionalization of Nonactivated C(sp)-H Bonds.通过非活化 C(sp3)-H 键的 C-H 功能化合成内酯。
Org Lett. 2016 Dec 16;18(24):6472-6475. doi: 10.1021/acs.orglett.6b03371. Epub 2016 Dec 5.
4
Copper-Catalyzed Bromination of C(sp )-H Bonds Distal to Functional Groups.铜催化的 C(sp )-H 键与功能基团远端的溴化反应。
Angew Chem Int Ed Engl. 2017 Jan 2;56(1):306-309. doi: 10.1002/anie.201608210. Epub 2016 Nov 29.
5
Catalytic alkylation of remote C-H bonds enabled by proton-coupled electron transfer.质子耦合电子转移实现的远程C-H键催化烷基化反应。
Nature. 2016 Nov 10;539(7628):268-271. doi: 10.1038/nature19811. Epub 2016 Oct 12.
6
Amide-directed photoredox-catalysed C-C bond formation at unactivated sp C-H bonds.酰胺导向的光氧化还原催化未活化sp C-H键处的C-C键形成。
Nature. 2016 Nov 10;539(7628):272-275. doi: 10.1038/nature19810. Epub 2016 Oct 12.
7
Ligand-accelerated enantioselective methylene C(sp3)-H bond activation.配体加速的对映选择性亚甲基C(sp3)-H键活化
Science. 2016 Sep 2;353(6303):1023-1027. doi: 10.1126/science.aaf4434.
8
Triiodide-Mediated δ-Amination of Secondary C-H Bonds.三碘化物介导的仲 C-H 键的 δ-氨基化反应。
Angew Chem Int Ed Engl. 2016 Aug 16;55(34):9974-8. doi: 10.1002/anie.201604704. Epub 2016 Jul 7.
9
Dual Catalysis Strategies in Photochemical Synthesis.光化学合成中的双催化策略
Chem Rev. 2016 Sep 14;116(17):10035-74. doi: 10.1021/acs.chemrev.6b00018. Epub 2016 Apr 25.
10
Ligand-Enabled Arylation of γ-C-H Bonds.配体促进的γ-C-H键芳基化反应
Angew Chem Int Ed Engl. 2016 Mar 18;55(13):4317-21. doi: 10.1002/anie.201512020. Epub 2016 Feb 25.
Zotero 插件