光氧化还原介导的净中性自由基/极性交叉反应。
Photoredox-Mediated Net-Neutral Radical/Polar Crossover Reactions.
作者信息
Wiles Rebecca J, Molander Gary A
机构信息
Department of Chemistry, University of Pennsylvania, 231 S. 34 St. Philadelphia, PA 19104.
出版信息
Isr J Chem. 2020 Mar;60(3-4):281-293. doi: 10.1002/ijch.201900166. Epub 2020 Feb 18.
Abstract
Radical/Polar Crossover (RPC) chemistry is a rapidly growing subset of photoredox catalysis that is characterized by transformations featuring both radical and ionic modes of reactivity. Net-neutral RPC is particularly interesting in that both the single-electron oxidation and reduction steps occur through interaction with the photocatalyst, thus precluding the need for exogenous oxidants or reductants. As such, these transformations facilitate rapid incorporation of molecular complexity while maintaining mild reaction conditions. This review covers recent advances in photoredox-mediated net-neutral RPC synthetic methods, with a particular emphasis on C-C bond-forming reactions.
摘要
自由基/极性交叉（RPC）化学是光氧化还原催化中一个快速发展的分支，其特点是反应同时具有自由基和离子反应模式。净中性RPC尤其引人关注，因为单电子氧化和还原步骤均通过与光催化剂相互作用发生，从而无需外源氧化剂或还原剂。因此，这些反应在保持温和反应条件的同时，能够快速引入分子复杂性。本综述涵盖了光氧化还原介导的净中性RPC合成方法的最新进展，特别着重于碳-碳键形成反应。
相似文献
1
Photoredox-Mediated Net-Neutral Radical/Polar Crossover Reactions.光氧化还原介导的净中性自由基/极性交叉反应。
Isr J Chem. 2020 Mar;60(3-4):281-293. doi: 10.1002/ijch.201900166. Epub 2020 Feb 18.
2
Synthetic and Mechanistic Implications of Chlorine Photoelimination in Nickel/Photoredox C(sp)-H Cross-Coupling.镍/光氧化还原 C(sp)-H 交叉偶联中氯光消除的合成和机理意义。
Acc Chem Res. 2021 Feb 16;54(4):988-1000. doi: 10.1021/acs.accounts.0c00694. Epub 2021 Jan 29.
3
Photoredox-Catalyzed Multicomponent Synthesis of Functionalized γ-Amino Butyric Acids via Reductive Radical Polar Crossover.光氧化还原催化的通过还原自由基极性交叉的官能化 γ-氨基丁酸的多组分合成。
Org Lett. 2023 May 19;25(19):3429-3434. doi: 10.1021/acs.orglett.3c00991. Epub 2023 May 10.
4
Merging Carbonyl Addition with Photocatalysis.羰基加成与光催化的融合。
Acc Chem Res. 2022 Apr 19;55(8):1135-1147. doi: 10.1021/acs.accounts.1c00799. Epub 2022 Mar 31.
5
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.
6
Direct Synthesis of 2-Hydroxytrifluoroethylacetophenones via Organophotoredox-Mediated Net-Neutral Radical/Polar Crossover.通过有机光氧化还原介导的净中性自由基/极性交叉直接合成2-羟基三氟乙基苯乙酮
J Org Chem. 2024 Aug 16;89(16):11682-11692. doi: 10.1021/acs.joc.4c01419. Epub 2024 Aug 1.
7
Photoredox Radical/Polar Crossover Enables Construction of Saturated Nitrogen Heterocycles.光氧化还原自由基/极性交叉实现饱和氮杂环的构建。
Org Lett. 2019 Apr 5;21(7):2317-2321. doi: 10.1021/acs.orglett.9b00602. Epub 2019 Mar 12.
8
Merging Visible Light Photoredox and Gold Catalysis.可见光光氧化还原与金催化的融合。
Acc Chem Res. 2016 Oct 18;49(10):2261-2272. doi: 10.1021/acs.accounts.6b00351. Epub 2016 Sep 9.
9
Free Radical Chemistry Enabled by Visible Light-Induced Electron Transfer.可见光诱导电子转移引发自由基化学。
Acc Chem Res. 2016 Oct 18;49(10):2295-2306. doi: 10.1021/acs.accounts.6b00270. Epub 2016 Aug 16.
10
Photoredox radical/polar crossover enables C-H -difunctionalization of 1,3-benzodioxoles for the synthesis of monofluorocyclohexenes.光氧化还原自由基/极性交叉反应实现了1,3-苯并二恶唑的C-H双官能团化反应，用于合成单氟环己烯。
Chem Sci. 2023 May 12;14(22):6045-6051. doi: 10.1039/d3sc00912b. eCollection 2023 Jun 7.
引用本文的文献
1
Modular reductive radical-polar crossover-based acyl migration reactions of -vinylimides with alkyl, silyl, and acyl radicals.基于模块化还原自由基-极性交叉的乙烯基酰亚胺与烷基、硅基和酰基自由基的酰基迁移反应。
RSC Adv. 2025 Apr 15;15(15):11582-11586. doi: 10.1039/d5ra01542a. eCollection 2025 Apr 9.
2
Natural Product Synthesis Enabled by Radical-Polar Crossover Reactions.基于自由基-极性交叉反应的天然产物合成
J Org Chem. 2025 Apr 18;90(15):5083-5092. doi: 10.1021/acs.joc.5c00306. Epub 2025 Apr 4.
3
Photoredox/Cr-catalyzed enantioselective radical-polar crossover transformation via C-H functionalization.通过C-H官能化实现的光氧化还原/铬催化对映选择性自由基-极性交叉转化。
Nat Commun. 2025 Feb 4;16(1):1354. doi: 10.1038/s41467-025-56372-1.
4
Organophotoredox-Driven Three-Component Synthesis of β-Trifluoromethyl β-Amino Ketones†.光催化氧化还原驱动的β-三氟甲基β-氨基酮的三组分合成†
J Org Chem. 2025 Feb 14;90(6):2500-2509. doi: 10.1021/acs.joc.4c03142. Epub 2025 Jan 30.
5
Chemodivergent dearomatization of benzene-linked O-oxime esters EnT-induced radical cross-coupling.苯环相连的 O-肟酯的化学发散性脱芳构化：EnT 诱导的自由基交叉偶联
Chem Sci. 2025 Jan 9;16(6):2690-2699. doi: 10.1039/d4sc07681h. eCollection 2025 Feb 5.
6
Alkene Carboxy-Alkylation via CO通过一氧化碳实现烯烃的羧基烷基化
J Am Chem Soc. 2024 Dec 25;146(51):35035-35042. doi: 10.1021/jacs.4c14421. Epub 2024 Dec 12.
7
Direct Synthesis of 2-Hydroxytrifluoroethylacetophenones via Organophotoredox-Mediated Net-Neutral Radical/Polar Crossover.通过有机光氧化还原介导的净中性自由基/极性交叉直接合成2-羟基三氟乙基苯乙酮
J Org Chem. 2024 Aug 16;89(16):11682-11692. doi: 10.1021/acs.joc.4c01419. Epub 2024 Aug 1.
8
Synthesis of constrained bicycloalkanes through bibase-promoted brook rearrangement/radical-polar crossover cyclization.通过双碱促进的布鲁克重排/自由基-极性交叉环化反应合成受限双环烷烃。
Chem Sci. 2024 Jun 13;15(28):11092-11098. doi: 10.1039/d4sc02532f. eCollection 2024 Jul 17.
9
Total syntheses of (-)-macrocalyxoformins A and B and (-)-ludongnin C.(-)-macrocalyxoformins A 和 B 以及 (-)-ludongnin C 的全合成。
Nat Commun. 2024 Jul 18;15(1):6052. doi: 10.1038/s41467-024-50374-1.
10
Photocascade chemoselective controlling of ambident thio(seleno)cyanates with alkenes via catalyst modulation.通过催化剂调控实现烯烃对硫（硒）氰酸酯的光级联化学选择性控制。
Nat Commun. 2024 Jul 9;15(1):5739. doi: 10.1038/s41467-024-49279-w.
本文引用的文献
1
Advancements in Visible-Light-Enabled Radical C(sp)2-H Alkylation of (Hetero)arenes.可见光促进的（杂）芳烃C(sp)2-H自由基烷基化反应的进展
Synthesis (Stuttg). 2019 Mar;51(5):1063-1072. doi: 10.1055/s-0037-1611658. Epub 2019 Jan 25.
2
Reductive radical-polar crossover: traditional electrophiles in modern radical reactions.还原自由基-极性交叉：现代自由基反应中的传统亲电试剂。
Chem Sci. 2019 Aug 16;10(36):8285-8291. doi: 10.1039/c9sc03359a. eCollection 2019 Sep 28.
3
Metal-free defluorinative arylation of trifluoromethyl alkenes via photoredox catalysis.通过光氧化还原催化实现三氟甲基烯烃的无金属脱氟芳基化反应。
Chem Commun (Camb). 2019 Jul 7;55(53):7599-7602. doi: 10.1039/c9cc04265b. Epub 2019 Jun 14.
4
Photocatalytic carbanion generation - benzylation of aliphatic aldehydes to secondary alcohols.光催化碳负离子生成——脂肪醛苄基化制备仲醇
Chem Sci. 2019 Apr 16;10(19):5162-5166. doi: 10.1039/c9sc01356c. eCollection 2019 May 21.
5
SOF-mediated transformation of 2'-hydroxyacetophenones to benzo-oxetes.索非布韦介导的2'-羟基苯乙酮向苯并氧杂环丁烷的转化。
Beilstein J Org Chem. 2019 Apr 25;15:976-980. doi: 10.3762/bjoc.15.95. eCollection 2019.
6
Deaminative Reductive Arylation Enabled by Nickel/Photoredox Dual Catalysis.镍/光氧化还原双催化促进的脱氨还原芳基化反应。
Org Lett. 2019 May 3;21(9):3346-3351. doi: 10.1021/acs.orglett.9b01097. Epub 2019 Apr 17.
7
Photocatalytic, Phosphoranyl Radical-Mediated N-O Cleavage of Strained Cycloketone Oximes.光催化、磷酰基自由基介导的环张力酮肟的N-O键裂解
Org Lett. 2019 Apr 19;21(8):2658-2662. doi: 10.1021/acs.orglett.9b00651. Epub 2019 Apr 3.
8
Photoredox Radical/Polar Crossover Enables Construction of Saturated Nitrogen Heterocycles.光氧化还原自由基/极性交叉实现饱和氮杂环的构建。
Org Lett. 2019 Apr 5;21(7):2317-2321. doi: 10.1021/acs.orglett.9b00602. Epub 2019 Mar 12.
9
Photoredox-Catalyzed Cyclobutane Synthesis by a Deboronative Radical Addition-Polar Cyclization Cascade.通过脱硼自由基加成-极性环化级联反应实现光氧化还原催化的环丁烷合成
Angew Chem Int Ed Engl. 2019 Mar 18;58(12):3870-3874. doi: 10.1002/anie.201813917. Epub 2019 Feb 15.
10
Biaryl synthesis with arenediazonium salts: cross-coupling, CH-arylation and annulation reactions.芳基重氮盐参与的联芳基合成：交叉偶联、C-H芳基化及环化反应
Chem Soc Rev. 2019 Feb 18;48(4):1150-1193. doi: 10.1039/c8cs00453f.
Zotero 插件