氮自由基前体引发的 δ-C-H 卤化反应。
δ-C-H Halogenation Reactions Enabled by a Nitrogen-Centered Radical Precursor.
机构信息
Department of Chemistry, The Scripps Research Institute, La Jolla, California 92037, United States.
出版信息
Org Lett. 2022 May 27;24(20):3652-3656. doi: 10.1021/acs.orglett.2c01261. Epub 2022 May 13.
Abstract
Nitrogen-centered radicals are versatile synthetic intermediates with the ability to undergo diverse reactions such as hydrogen atom transfer (HAT), β-scission, and addition across unsaturated systems. A long-standing impediment to the wider adoption of these intermediates in synthesis has been the difficulty of their generation. Herein we disclose a new hydrazonyl carboxylic acid precursor to nitrogen-centered radicals and its application toward remote C-H fluorination and chlorination reactions of sulfonyl-protected alkyl amines via 1,5-HAT.
摘要
氮中心自由基是多功能的合成中间体，能够进行多种反应，如氢原子转移 (HAT)、β 断裂和在不饱和系统中的加成。这些中间体在合成中广泛应用的一个长期障碍是它们的生成难度。在此，我们公开了一种新的氮中心自由基的酰肼羧酸前体及其在通过 1,5-HAT 进行磺酰基保护的烷基胺的远程 C-H 氟化和氯化反应中的应用。
相似文献
1
δ-C-H Halogenation Reactions Enabled by a Nitrogen-Centered Radical Precursor.氮自由基前体引发的 δ-C-H 卤化反应。
Org Lett. 2022 May 27;24(20):3652-3656. doi: 10.1021/acs.orglett.2c01261. Epub 2022 May 13.
2
Sulfamate Esters Guide Selective Radical-Mediated Chlorination of Aliphatic C-H Bonds.磺酰胺酯指导选择性的自由基介导的脂肪族 C-H 键氯化反应。
Angew Chem Int Ed Engl. 2018 Jan 2;57(1):296-299. doi: 10.1002/anie.201710322. Epub 2017 Dec 7.
3
When Light Meets Nitrogen-Centered Radicals: From Reagents to Catalysts.当光遇到含氮自由基：从试剂到催化剂。
Acc Chem Res. 2020 May 19;53(5):1066-1083. doi: 10.1021/acs.accounts.0c00090. Epub 2020 Apr 14.
4
Photoinduced Remote Functionalization of Amides and Amines Using Electrophilic Nitrogen Radicals.利用亲电氮自由基实现酰胺和胺的光诱导远程官能团化
Angew Chem Int Ed Engl. 2018 Sep 24;57(39):12945-12949. doi: 10.1002/anie.201807941. Epub 2018 Aug 29.
5
Applications of Radical Carbonylation and Amine Addition Chemistry: 1,4-Hydrogen Transfer of 1-Hydroxylallyl Radicals.自由基羰基化和胺加成化学的应用：1-羟基烯丙基自由基的1,4-氢转移
Acc Chem Res. 2018 Sep 18;51(9):2023-2035. doi: 10.1021/acs.accounts.8b00278. Epub 2018 Aug 23.
6
δ-C-H Mono- and Dihalogenation of Alcohols.醇的δ-C-H单卤化和二卤化
J Am Chem Soc. 2020 Feb 12;142(6):2766-2770. doi: 10.1021/jacs.9b13171. Epub 2020 Jan 30.
7
Modifying Positional Selectivity in C-H Functionalization Reactions with Nitrogen-Centered Radicals: Generalizable Approaches to 1,6-Hydrogen-Atom Transfer Processes.利用含氮自由基修饰C-H官能化反应中的位置选择性：1,6-氢原子转移过程的通用方法
Synlett. 2020 Jan;31(2):102-116. doi: 10.1055/s-0039-1691501. Epub 2019 Nov 27.
8
Generation of Aromatic N-Heterocyclic Radicals for Functionalization of Unactivated Alkenes.用于未活化烯烃官能化的芳族氮杂环自由基的生成
Angew Chem Int Ed Engl. 2023 Dec 21;62(52):e202314312. doi: 10.1002/anie.202314312. Epub 2023 Nov 22.
9
Recent Insights on Hydrogen Atom Transfer in the Inhibition of Hydrocarbon Autoxidation.关于抑制碳氢化合物自动氧化过程中氢原子转移的最新见解。
Acc Chem Res. 2018 Sep 18;51(9):1996-2005. doi: 10.1021/acs.accounts.8b00251. Epub 2018 Jul 23.
10
Synthetic Utilization of α-Aminoalkyl Radicals and Related Species in Visible Light Photoredox Catalysis.可见光光氧化还原催化中 α-氨烷基自由基及相关物种的合成利用。
Acc Chem Res. 2016 Sep 20;49(9):1946-56. doi: 10.1021/acs.accounts.6b00251. Epub 2016 Aug 9.
引用本文的文献
1
Recent advances in amidyl radical-mediated photocatalytic direct intermolecular hydrogen atom transfer.酰胺基自由基介导的光催化直接分子间氢原子转移的最新进展。
Beilstein J Org Chem. 2025 Jun 27;21:1306-1323. doi: 10.3762/bjoc.21.100. eCollection 2025.
2
Regioselective Rearrangement of Nitrogen- and Carbon-Centered Radical Intermediates in the Hofmann-Löffler-Freytag Reaction.霍夫曼-勒夫勒-弗雷泰格反应中氮中心和碳中心自由基中间体的区域选择性重排
J Phys Chem A. 2024 Apr 4;128(13):2574-2583. doi: 10.1021/acs.jpca.3c07892. Epub 2024 Mar 22.
本文引用的文献
1
Illuminating Photoredox Catalysis.光致氧化还原催化
Trends Chem. 2019 Apr;1(1):111-125. doi: 10.1016/j.trechm.2019.01.008. Epub 2019 Feb 22.
2
Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis.质子耦合电子转移在有机合成中的光化学和电化学应用。
Chem Rev. 2022 Jan 26;122(2):2017-2291. doi: 10.1021/acs.chemrev.1c00374. Epub 2021 Nov 23.
3
Strategies to Generate Nitrogen-centered Radicals That May Rely on Photoredox Catalysis: Development in Reaction Methodology and Applications in Organic Synthesis.氮中心自由基的生成策略可能依赖于光氧化还原催化：反应方法的发展及其在有机合成中的应用。
Chem Rev. 2022 Jan 26;122(2):2353-2428. doi: 10.1021/acs.chemrev.1c00444. Epub 2021 Oct 8.
4
N-Directed fluorination of unactivated Csp-H bonds.未活化Csp-H键的N-导向氟化反应。
Chem Sci. 2019 Dec 16;11(4):1102-1106. doi: 10.1039/c9sc04055b.
5
Sulfamides direct radical-mediated chlorination of aliphatic C-H bonds.磺胺类化合物可直接实现自由基介导的脂肪族碳氢键氯化反应。
Chem Sci. 2019 Nov 8;11(1):217-223. doi: 10.1039/c9sc03428e.
6
Visible light photoredox-catalysed remote C-H functionalisation enabled by 1,5-hydrogen atom transfer (1,5-HAT).可见光光氧化还原催化远程 C-H 官能化反应，由 1,5-氢原子转移（1,5-HAT）引发。
Chem Soc Rev. 2021 Jul 7;50(13):7359-7377. doi: 10.1039/d0cs00774a. Epub 2021 May 20.
7
Photoredox-Mediated Mono- and Difluorination of Remote Unactivated Methylene C(sp)-H Bonds of -Alkyl Sulfonamides.光氧化还原介导的 - 烷基磺酰胺中远程非活化亚甲基 C(sp 3 )-H 键的单氟和双氟化反应。
Org Lett. 2021 May 7;23(9):3631-3635. doi: 10.1021/acs.orglett.1c01020. Epub 2021 Apr 21.
8
Photoinduced Site-Selective C(sp)-H Chlorination of Aliphatic Amides.脂肪族酰胺的光诱导位点选择性C(sp)-H氯化反应
Org Lett. 2020 Nov 20;22(22):8899-8903. doi: 10.1021/acs.orglett.0c03297. Epub 2020 Nov 11.
9
Current Contributions of Organofluorine Compounds to the Agrochemical Industry.有机氟化合物对农用化学品行业的当前贡献。
iScience. 2020 Aug 18;23(9):101467. doi: 10.1016/j.isci.2020.101467. eCollection 2020 Sep 25.
10
Iodine Catalysis for C(sp )-H Fluorination with a Nucleophilic Fluorine Source.碘催化亲核氟源用于C(sp) -H氟化反应
Angew Chem Int Ed Engl. 2020 Aug 17;59(34):14241-14245. doi: 10.1002/anie.202004902. Epub 2020 Jul 10.
Zotero 插件