通过使用酰亚胺氯试剂进行多杂原子 Cope 重排反应实现酮硝酮的 α-胺化。
α-Amination of keto-nitrones via multihetero-Cope rearrangement employing an imidoyl chloride reagent.
机构信息
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, USA.
出版信息
Chem Commun (Camb). 2012 Aug 7;48(61):7568-70. doi: 10.1039/c2cc33401a. Epub 2012 Jun 26.
Abstract
α-Aminations of ketone-derived nitrones have been developed via [3,3]-rearrangement of the intermediates generated upon condensation with imidoyl chlorides. Careful reagent selection provides synthetically attractive amino protecting groups. The enediamide or α'-carbamoyl enamide products can be hydrolyzed to the desired carbonyl, or exposed to electrophiles for further α-functionalization.
摘要
通过与亚酰氯缩合生成的中间体的[3,3]-重排，开发了酮衍生硝酮的α-氨基化反应。仔细选择试剂可以提供有吸引力的氨基保护基。所得的烯二酰胺或α'-氨甲酰基烯酰胺产物可以水解得到所需的羰基化合物，或者暴露于亲电试剂进一步进行α-官能化。
相似文献
1
α-Amination of keto-nitrones via multihetero-Cope rearrangement employing an imidoyl chloride reagent.通过使用酰亚胺氯试剂进行多杂原子 Cope 重排反应实现酮硝酮的 α-胺化。
Chem Commun (Camb). 2012 Aug 7;48(61):7568-70. doi: 10.1039/c2cc33401a. Epub 2012 Jun 26.
2
Formation of Complex α-Imino Esters via Multihetero-Cope Rearrangement of α-Keto Ester Derived Nitrones.通过α-酮酯衍生硝酮的多杂原子-Cope重排形成复杂的α-亚氨基酯
Synthesis (Stuttg). 2019 Jan;51(1):203-212. doi: 10.1055/s-0037-1610391. Epub 2018 Dec 6.
3
Catalytically Generated Vanadium Enolates Formed via Interruption of the Meyer-Schuster Rearrangement as Useful Reactive Intermediates.通过中断迈耶-舒斯特重排催化生成的钒烯醇盐作为有用的反应中间体。
Acc Chem Res. 2020 Aug 18;53(8):1568-1579. doi: 10.1021/acs.accounts.0c00285. Epub 2020 Jul 21.
4
[The chemistry of pericyclic reactions and their application to syntheses of heterocyclic compounds].[周环反应的化学及其在杂环化合物合成中的应用]
Yakugaku Zasshi. 2003 Sep;123(9):717-59. doi: 10.1248/yakushi.123.717.
5
α-Imino Iridium Carbenes from Imidoyl Sulfoxonium Ylides: Application in the One-Step Synthesis of Indoles.来自亚胺基硫鎓叶立德的α-亚氨基铱卡宾：在吲哚一步合成中的应用
J Org Chem. 2020 Jun 5;85(11):7433-7445. doi: 10.1021/acs.joc.0c00833. Epub 2020 May 7.
6
Stereoselective synthesis of 2-alkylidene-3-iminoindoles by reaction of 1,1-dianions with oxalic acid bis(imidoyl) chlorides.通过1,1 - 双负离子与草酸双（亚氨酰）氯化物反应立体选择性合成2 - 亚烷基 - 3 - 亚氨基吲哚。
J Org Chem. 2000 Jun 16;65(12):3603-11. doi: 10.1021/jo991701l.
7
Asymmetric Catalytic Rearrangements with α-Diazocarbonyl Compounds.α-重氮羰基化合物的不对称催化重排反应。
Acc Chem Res. 2022 Feb 1;55(3):415-428. doi: 10.1021/acs.accounts.1c00664. Epub 2022 Jan 14.
8
Gold-catalyzed 1,2-iminonitronation of electron-deficient alkynes with nitrosoarenes to afford α-imidoyl nitrones.金催化缺电子炔烃与亚硝基芳烃进行1,2-亚氨基硝化反应以生成α-亚氨基硝酮。
Chem Commun (Camb). 2014 Dec 28;50(100):15864-6. doi: 10.1039/c4cc06962e.
9
Indium chloride catalyzed alkylative rearrangement of propargylic acetates using alkyl chlorides, alcohols, and acetates: facile synthesis of α-alkyl-α,β-unsaturated carbonyl compounds.氯化铟催化炔丙基乙酸酯与氯代烃、醇和乙酸盐的烷基化重排反应：α-烷基-α,β-不饱和羰基化合物的简便合成。
Org Lett. 2014 Feb 21;16(4):1176-9. doi: 10.1021/ol500046e. Epub 2014 Feb 4.
10
Catalytic reductive aminations using molecular hydrogen for synthesis of different kinds of amines.使用分子氢进行催化还原胺化反应合成各种胺类。
Chem Soc Rev. 2020 Sep 7;49(17):6273-6328. doi: 10.1039/c9cs00286c. Epub 2020 Jul 30.
引用本文的文献
1
Development of New Reactions Driven by N-O Bond Cleavage: from -Acyl Hydroxylamines to Tetrodotoxin.由N-O键裂解驱动的新反应的开发：从α-酰基羟胺到河豚毒素。
Synlett. 2023 Aug;34(13):1563-1572. doi: 10.1055/s-0042-1751423. Epub 2023 Feb 23.
2
Formation of Complex α-Imino Esters via Multihetero-Cope Rearrangement of α-Keto Ester Derived Nitrones.通过α-酮酯衍生硝酮的多杂原子-Cope重排形成复杂的α-亚氨基酯
Synthesis (Stuttg). 2019 Jan;51(1):203-212. doi: 10.1055/s-0037-1610391. Epub 2018 Dec 6.
本文引用的文献
1
Highly enantioselective organocatalytic α-amination reactions of aryl oxindoles: developing designer multifunctional alkaloid catalysts.高对映选择性的芳基氧化吲哚的有机催化α-胺化反应：设计多功能生物碱催化剂。
Org Lett. 2010 Dec 17;12(24):5696-9. doi: 10.1021/ol102493q. Epub 2010 Nov 11.
2
Rearrangement strategy for the synthesis of 2-aminoanilines.合成 2-氨基苯胺的重排策略。
Org Lett. 2010 Apr 2;12(7):1492-5. doi: 10.1021/ol100196a.
3
Catalytic asymmetric synthesis of 3-aminooxindoles: enantiofacial selectivity switch in bimetallic vs monometallic Schiff base catalysis.手性双金属席夫碱与单金属席夫碱催化不对称合成 3-氨基氧吲哚：对映选择性开关。
J Am Chem Soc. 2010 Feb 3;132(4):1255-7. doi: 10.1021/ja908906n.
4
Expanding the scope of cinchona alkaloid-catalyzed enantioselective alpha-aminations of oxindoles: a versatile approach to optically active 3-amino-2-oxindole derivatives.拓展金鸡纳生物碱催化的吲哚酮对映选择性 α-氨基化反应的范围：一种构建光学活性 3-氨基-2-吲哚酮衍生物的通用方法。
J Org Chem. 2009 Dec 4;74(23):8935-8. doi: 10.1021/jo902039a.
5
Asymmetric construction of quaternary stereocenters by direct organocatalytic amination of 3-substituted oxindoles.通过 3-取代的吲哚啉的直接有机催化氨化反应构建季立体中心的不对称合成。
Chem Commun (Camb). 2009 Nov 28(44):6753-5. doi: 10.1039/b915257a. Epub 2009 Sep 25.
6
[3,3]-Sigmatropic rearrangements: recent applications in the total synthesis of natural products.[3,3]-σ重排反应：在天然产物全合成中的最新应用。
Chem Soc Rev. 2009 Nov;38(11):3133-48. doi: 10.1039/b901177n. Epub 2009 Sep 2.
7
Simple reaction conditions for the formation of ketonitrones from ketones and hydroxylamines.酮肟由酮和羟胺形成的简单反应条件。
J Org Chem. 2009 Nov 6;74(21):8381-3. doi: 10.1021/jo901653d.
8
Highly enantioselective and organocatalytic alpha-amination of 2-oxindoles.2-氧化吲哚的高对映选择性有机催化α-胺化反应
Org Lett. 2009 Sep 3;11(17):3874-7. doi: 10.1021/ol901405r.
9
A novel one-pot procedure for the stereoselective synthesis of alpha-hydroxy esters from ortho esters.一种从邻酯立体选择性合成α-羟基酯的新颖一锅法。
Org Lett. 2009 Sep 17;11(18):4032-5. doi: 10.1021/ol901214n.
10
Direct asymmetric alpha-amination of cyclic ketones catalyzed by siloxyproline.硅氧基脯氨酸催化环状酮的直接不对称α-胺化反应
Chem Asian J. 2008 Feb 1;3(2):225-32. doi: 10.1002/asia.200700307.
Zotero 插件