使用有机光氧化还原催化剂实现脂肪族和芳香族-α-酰基腙的烷基自由基加成反应。
Alkyl Radical Addition to Aliphatic and Aromatic -Acylhydrazones Using an Organic Photoredox Catalyst.
机构信息
Department of Chemistry , University of Iowa , Iowa City , Iowa 52242 , United States.
出版信息
Org Lett. 2019 Oct 18;21(20):8290-8294. doi: 10.1021/acs.orglett.9b03053. Epub 2019 Sep 27.
Abstract
Increased versatility of intermolecular radical addition to imino acceptors via photoredox catalysis is reported. Primary and secondary radicals, generated via visible-light photocatalysis from alkyl biscatecholatosilicates with organocatalyst 4CzIPN, add successfully to both aromatic and aliphatic -acylhydrazones in the presence of MgCl. With -benzoylhydrazones, a simple reductive cleavage of the N-N bond of the hydrazine adduct furnishes the free amine. Synthetic utility is exemplified in a synthetic application toward repaglinide, a clinically important hypoglycemic agent.
摘要
通过光氧化还原催化，报道了亚胺受体的分子间自由基加成反应的多功能性增加。通过可见光光催化，从烷基双邻苯二酚硅酸酯中生成的伯和仲自由基，在有机催化剂 4CzIPN 和 MgCl 的存在下，成功地添加到芳族和脂肪族酰基腙中。对于 -苯甲酰基腙，肼加合物的 N-N 键的简单还原裂解提供了游离胺。在合成应用中，以瑞格列奈为例，这是一种临床上重要的降血糖药物，说明了其合成实用性。
相似文献
1
Alkyl Radical Addition to Aliphatic and Aromatic -Acylhydrazones Using an Organic Photoredox Catalyst.使用有机光氧化还原催化剂实现脂肪族和芳香族-α-酰基腙的烷基自由基加成反应。
Org Lett. 2019 Oct 18;21(20):8290-8294. doi: 10.1021/acs.orglett.9b03053. Epub 2019 Sep 27.
2
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.
3
Radical additions to chiral hydrazones: stereoselectivity and functional group compatibility.对手性腙的自由基加成：立体选择性和官能团兼容性。
Top Curr Chem. 2012;320:61-91. doi: 10.1007/128_2011_163.
4
Photochemical Stereocontrol Using Tandem Photoredox-Chiral Lewis Acid Catalysis.光化学立体控制的串联光氧化还原-手性路易斯酸催化。
Acc Chem Res. 2016 Oct 18;49(10):2307-2315. doi: 10.1021/acs.accounts.6b00280. Epub 2016 Aug 9.
5
Mn-mediated coupling of alkyl iodides and chiral N-acylhydrazones: optimization, scope, and evidence for a radical mechanism.锰介导的烷基碘化物与手性N-酰基腙的偶联反应：优化、范围及自由基机理的证据
J Org Chem. 2006 Sep 1;71(18):7016-27. doi: 10.1021/jo061158q.
6
The Prowess of Photogenerated Amine Radical Cations in Cascade Reactions: From Carbocycles to Heterocycles.光生胺自由基阳离子在级联反应中的卓越表现：从碳环到杂环。
Acc Chem Res. 2016 Sep 20;49(9):1957-68. doi: 10.1021/acs.accounts.6b00263. Epub 2016 Aug 18.
7
Indium-mediated catalytic enantioselective allylation of N-benzoylhydrazones using a protonated chiral amine.铟介导的质子化手性伯胺催化 N-苯甲酰腙的对映选择性烯丙基化反应。
J Am Chem Soc. 2010 Sep 8;132(35):12168-9. doi: 10.1021/ja1035336.
8
Radical carbon-carbon bond formations enabled by visible light active photocatalysts.可见光活性光催化剂实现的碳-碳键的自由基形成反应。
Chimia (Aarau). 2012;66(6):394-8. doi: 10.2533/chimia.2012.394.
9
Intermolecular radical addition to N-acylhydrazones as a stereocontrol strategy for alkaloid synthesis: formal synthesis of quinine.分子间自由基加成到 N-酰腙作为生物碱合成的立体控制策略：奎宁的形式合成。
Org Biomol Chem. 2011 Jun 7;9(11):4039-43. doi: 10.1039/c1ob05219e. Epub 2011 May 3.
10
Control of asymmetry in the radical addition approach to chiral amine synthesis.手性胺合成的自由基加成方法中不对称性的控制
Top Curr Chem. 2014;343:1-32. doi: 10.1007/128_2013_481.
引用本文的文献
1
Photocatalytic Decarboxylative Alkylation of Cyclic Imine-BF Complexes: A Modular Route to Functionalized Azacycles.环状亚胺 - BF 配合物的光催化脱羧烷基化反应：一种合成功能化氮杂环的模块化方法。
J Am Chem Soc. 2024 Sep 25;146(38):26331-26339. doi: 10.1021/jacs.4c08754. Epub 2024 Sep 12.
2
Excited-state palladium-catalysed reductive alkylation of imines: scope and mechanism.激发态钯催化亚胺的还原烷基化反应：范围与机理
Chem Sci. 2022 Jul 7;13(29):8583-8589. doi: 10.1039/d2sc02363f. eCollection 2022 Jul 29.
3
Accessing Illusive Isomers of α-Ester Hydrazones via Visible-Light-Induced Pd-Catalyzed Heck-Type Alkylation.通过可见光诱导 Pd 催化 Heck 型烷基化反应来获取 α-酯腙的幻觉异构体。
Org Lett. 2022 Jun 17;24(23):4176-4181. doi: 10.1021/acs.orglett.2c01409. Epub 2022 Jun 2.
4
First Evidence of Tris(catecholato)silicate Formation from Hydrolysis of an Alkyl Bis(catecholato)silicate.首次从烷基双（邻苯二酚酸根合）硅烷的水解产物中观察到硅酸三（邻苯二酚根合）的形成。
Molecules. 2022 Apr 14;27(8):2521. doi: 10.3390/molecules27082521.
5
Photoredox-Catalyzed Oxidation of Anions for the Atom-Economical Hydro-, Amido-, and Dialkylation of Alkenes.光氧化还原催化的阴离子氧化反应在烯烃的原子经济性的氢、酰胺和二烷基化反应中的应用。
J Org Chem. 2022 Mar 4;87(5):3498-3510. doi: 10.1021/acs.joc.1c03055. Epub 2022 Feb 8.
6
Diastereocontrol in Radical Addition to β-Benzyloxy Hydrazones: Revised Approach to Tubuvaline and Synthesis of -Benzyltubulysin V Benzyl Ester.β-苄氧基腙的立体选择性自由基加成：tubuvaline 的新方法及 -苄基tubulysin V 苄酯的合成。
J Org Chem. 2021 Nov 5;86(21):15139-15152. doi: 10.1021/acs.joc.1c01798. Epub 2021 Oct 12.
7
Stereoselective synthesis of unnatural α-amino acid derivatives through photoredox catalysis.通过光氧化还原催化实现非天然α-氨基酸衍生物的立体选择性合成。
Chem Sci. 2021 Mar 3;12(15):5430-5437. doi: 10.1039/d1sc00658d.
8
Synthesis of amino-diamondoid pharmacophores via photocatalytic C-H aminoalkylation.通过光催化 C-H 胺烷基化合成氨基类金刚石药效团。
Chem Commun (Camb). 2020 Aug 20;56(67):9699-9702. doi: 10.1039/d0cc02804e.
本文引用的文献
1
Olefin Amine (OLA) Reagents for the Synthesis of Bridged Bicyclic and Spirocyclic Saturated N-Heterocycles by Catalytic Hydrogen Atom Transfer (HAT) Reactions.通过催化氢原子转移（HAT）反应合成桥环双环和螺环饱和 N-杂环的烯烃胺（OLA）试剂。
J Am Chem Soc. 2019 Jun 19;141(24):9739-9745. doi: 10.1021/jacs.9b05074. Epub 2019 Jun 5.
2
Potassium Alkylpentafluorosilicates, Primary Alkyl Radical Precursors in the C-1 Alkylation of Tetrahydroisoquinolines.钾全氟戊基硅酸盐，四氢异喹啉 C-1 烷基化反应中的伯烷基自由基前体。
Org Lett. 2019 Jun 7;21(11):3981-3985. doi: 10.1021/acs.orglett.9b01124. Epub 2019 May 13.
3
Radical Addition to N-Tosylimines via C-H Activation Induced by Decatungstate Photocatalyst.通过十钨酸盐光催化剂诱导的C-H活化对N-甲苯磺酰亚胺进行自由基加成反应。
Org Lett. 2019 Jun 7;21(11):4271-4274. doi: 10.1021/acs.orglett.9b01450. Epub 2019 May 13.
4
Visible-Light-Mediated, Chemo- and Stereoselective Radical Process for the Synthesis of C-Glycoamino Acids.可见光介导的化学及立体选择性自由基过程合成C-糖基氨基酸
Org Lett. 2019 May 3;21(9):3086-3092. doi: 10.1021/acs.orglett.9b00724. Epub 2019 Apr 12.
5
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.
6
Photoinitiated Three-Component α-Perfluoroalkyl-β-heteroarylation of Unactivated Alkenes via Electron Catalysis.通过电子催化实现的光引发未活化烯烃的三组分α-全氟烷基-β-杂芳基化反应
Org Lett. 2019 Jan 4;21(1):325-329. doi: 10.1021/acs.orglett.8b03849. Epub 2018 Dec 21.
7
Branch-Selective Addition of Unactivated Olefins into Imines and Aldehydes.未活化烯烃对亚胺和醛的支链选择性加成。
J Am Chem Soc. 2018 Dec 12;140(49):16976-16981. doi: 10.1021/jacs.8b11699. Epub 2018 Nov 29.
8
Copper(II)-Catalyzed Asymmetric Photoredox Reactions: Enantioselective Alkylation of Imines Driven by Visible Light.铜（II）催化的不对称光氧化还原反应：可见光驱动的亚胺对映选择性烷基化反应
J Am Chem Soc. 2018 Nov 21;140(46):15850-15858. doi: 10.1021/jacs.8b09251. Epub 2018 Oct 29.
9
A General Amino Acid Synthesis Enabled by Innate Radical Cross-Coupling.由固有自由基交叉偶联作用实现的一般氨基酸合成。
Angew Chem Int Ed Engl. 2018 Oct 26;57(44):14560-14565. doi: 10.1002/anie.201809310. Epub 2018 Oct 15.
10
Radicals in natural product synthesis.天然产物合成中的自由基。
Chem Soc Rev. 2018 Oct 29;47(21):7851-7866. doi: 10.1039/c8cs00379c.
Zotero 插件