质子添加剂在铜催化的双活化亲双烯体不对称狄尔斯-阿尔德环加成反应中的作用：迈向麦哲伦型石松生物碱的合成
Effect of protic additives in Cu-catalysed asymmetric Diels-Alder cycloadditions of doubly activated dienophiles: towards the synthesis of magellanine-type Lycopodium alkaloids.
作者信息
Lindsay Vincent N G, Murphy Rebecca A, Sarpong Richmond
机构信息
Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695, USA.
出版信息
Chem Commun (Camb). 2017 Sep 14;53(74):10291-10294. doi: 10.1039/c7cc06367a.
Abstract
The pronounced beneficial effect of a precise amount of protic additive in an enantioselective Cu-catalysed Diels-Alder reaction is reported. This reaction, which employs a cyclic alkylidene β-ketoester as a dienophile, represents one of the first examples of a transformation where these extremely versatile, though highly unstable reaction partners participate effectively in catalytic asymmetric cycloaddition with a functionalised diene. The cycloadduct was used as an intermediate towards the synthesis of magellanine-type Lycopodium alkaloids featuring a Stille cross-coupling of a highly congested enol triflate and a unique Meinwald rearrangement/cyclopropanation sequence.
摘要
据报道，在对映选择性铜催化的狄尔斯-阿尔德反应中，精确量的质子添加剂具有显著的有益效果。该反应使用环状亚烷基β-酮酯作为亲双烯体，是这些极其通用但高度不稳定的反应伙伴有效参与与官能化二烯的催化不对称环加成反应的首批转化实例之一。环加成产物被用作合成麦哲伦型石松生物碱的中间体，该合成过程具有高度拥挤的烯醇三氟甲磺酸酯的施蒂勒交叉偶联以及独特的迈恩瓦尔德重排/环丙烷化序列。
相似文献
1
Effect of protic additives in Cu-catalysed asymmetric Diels-Alder cycloadditions of doubly activated dienophiles: towards the synthesis of magellanine-type Lycopodium alkaloids.质子添加剂在铜催化的双活化亲双烯体不对称狄尔斯-阿尔德环加成反应中的作用：迈向麦哲伦型石松生物碱的合成
Chem Commun (Camb). 2017 Sep 14;53(74):10291-10294. doi: 10.1039/c7cc06367a.
2
Enantioselective oxa-Diels-Alder Sequences of Dendralenes.树状烯的对映选择性氧杂-狄尔斯-阿尔德反应序列
Angew Chem Int Ed Engl. 2022 Sep 26;61(39):e202204872. doi: 10.1002/anie.202204872. Epub 2022 Aug 19.
3
Molecular design principles towards -exclusive Diels-Alder reactions.用于专一性狄尔斯-阿尔德反应的分子设计原则。
RSC Adv. 2019 Mar 4;9(13):7246-7250. doi: 10.1039/c8ra10438g. eCollection 2019 Mar 1.
4
A Brief Review on Recent Developments in Diels-Alder Reactions.狄尔斯-阿尔德反应近期进展简述
Curr Org Synth. 2024 Jan 15. doi: 10.2174/0115701794262102231214074336.
5
Discovery and Surprises with Cyclizations, Cycloadditions, Fragmentations, and Rearrangements in Complex Settings.在复杂环境下的环化、环加成、碎裂和重排反应中的发现和惊喜。
Acc Chem Res. 2021 Feb 16;54(4):890-902. doi: 10.1021/acs.accounts.0c00814. Epub 2021 Feb 3.
6
(1R)-(+)-camphor and acetone derived alpha'-hydroxy enones in asymmetric Diels-Alder reaction: catalytic activation by Lewis and Brønsted acids, substrate scope, applications in syntheses, and mechanistic studies.(1R)-(+)-樟脑和丙酮衍生的 α'-羟基烯酮在不对称 Diels-Alder 反应中的应用：路易斯酸和布朗斯特酸的催化活化、底物范围、在合成中的应用以及机理研究。
J Org Chem. 2010 Mar 5;75(5):1458-73. doi: 10.1021/jo9023039.
7
Cross-conjugated Trienamine Catalysis with α'-Alkylidene 2-Cyclohexenones: Application in β,γ-Regioselective Aza-Diels-Alder Reaction.α'-亚烷基-2-环己烯酮的交叉共轭三烯胺催化：在β,γ-区域选择性氮杂狄尔斯-阿尔德反应中的应用
Chemistry. 2017 Feb 24;23(12):2945-2949. doi: 10.1002/chem.201605606. Epub 2017 Feb 1.
8
Intermolecular Diels-Alder Cycloaddition/Cross-Coupling Sequences of 2-Bromo-1,3-butadienes.2-溴-1,3-丁二烯的分子间 Diels-Alder 环加成/交叉偶联序列。
Org Lett. 2020 Feb 7;22(3):1022-1027. doi: 10.1021/acs.orglett.9b04567. Epub 2020 Jan 28.
9
Towards organo-click chemistry: development of organocatalytic multicomponent reactions through combinations of aldol, Wittig, Knoevenagel, Michael, Diels-Alder and Huisgen cycloaddition reactions.迈向有机点击化学：通过羟醛缩合、维蒂希反应、克诺文纳盖尔反应、迈克尔反应、狄尔斯-阿尔德反应和惠斯根环加成反应的组合开发有机催化多组分反应。
Chemistry. 2004 Oct 25;10(21):5323-31. doi: 10.1002/chem.200400597.
10
Expanding the Chiral Monoterpene Pool: Enantioselective Diels-Alder Reactions of α-Acyloxy Enones.拓展手性单萜库：α-烷氧基烯酮的对映选择性 Diels-Alder 反应。
Org Lett. 2022 Jun 3;24(21):3802-3806. doi: 10.1021/acs.orglett.2c01343. Epub 2022 May 20.
引用本文的文献
1
Synthetic Studies on Tetracyclic Diquinane Lycopodium Alkaloids Magellanine, Magellaninone and Paniculatine.四环二蒎烷石松生物碱麦哲伦碱、麦哲伦因酮和 paniculatine 的合成研究。
Molecules. 2023 Feb 3;28(3):1501. doi: 10.3390/molecules28031501.
2
Anionic Diels-Alder Chemistry of Cyclic Sodium Dien-1-olates Delivering Highly Stereoselective and Functionalized Polycyclic Adducts.环状1-烯醇钠的阴离子狄尔斯-阿尔德化学合成高立体选择性和官能化多环加合物
Org Lett. 2021 Aug 6;23(15):5709-5713. doi: 10.1021/acs.orglett.1c01807. Epub 2021 Jul 21.
本文引用的文献
1
A 11-Steps Total Synthesis of Magellanine through a Gold(I)-Catalyzed Dehydro Diels-Alder Reaction.通过金（I）催化的去氢 Diels-Alder 反应实现麦哲伦碱的 11 步全合成。
Angew Chem Int Ed Engl. 2017 May 22;56(22):6280-6283. doi: 10.1002/anie.201611606. Epub 2017 Jan 12.
2
P,S Ligands for the Asymmetric Construction of Quaternary Stereocenters in Palladium-Catalyzed Decarboxylative [4+2] Cycloadditions.钯催化脱羧[4+2]环加成反应中立体中心的不对称构建的 P,S 配体。
Angew Chem Int Ed Engl. 2016 Feb 5;55(6):2200-4. doi: 10.1002/anie.201509731. Epub 2016 Jan 6.
3
Network-analysis-guided synthesis of weisaconitine D and liljestrandinine.网络分析指导下的魏氏乌头碱D和利耶斯特兰定的合成。
Nature. 2015 Dec 24;528(7583):493-8. doi: 10.1038/nature16440.
4
Exceedingly Concise and Elegant Synthesis of (+)-Paniculatine, (-)-Magellanine, and (+)-Magellaninone.高度简洁优雅的 (+)-Paniculatine、(-)-Magellanine 和 (+)-Magellaninone 全合成。
Org Lett. 2015 Aug 7;17(15):3938-40. doi: 10.1021/acs.orglett.5b01975. Epub 2015 Jul 24.
5
Highly enantioselective catalytic asymmetric [2+2] cycloadditions of cyclic α-alkylidene β-oxo imides with ynamides.环状α-亚烷基β-氧代酰亚胺与烯炔酰胺的高度对映选择性催化不对称[2+2]环加成反应。
Chemistry. 2015 Feb 9;21(7):2798-802. doi: 10.1002/chem.201406189. Epub 2014 Dec 23.
6
Collective total synthesis of tetracyclic diquinane Lycopodium alkaloids (+)-paniculatine, (-)-magellanine, (+)-magellaninone and analogues thereof.四环二蒎烷石松生物碱（+）- paniculatine、（-）- magellanine、（+）- magellaninone 及其类似物的全合成。
Org Lett. 2014 Nov 7;16(21):5612-5. doi: 10.1021/ol502679v. Epub 2014 Oct 9.
7
Total synthesis of (+)-cassaine utilizing an anionic polycyclization strategy.利用阴离子多环化策略全合成 (+)-卡沙因。
Org Lett. 2013 Dec 20;15(24):6270-3. doi: 10.1021/ol4030937. Epub 2013 Dec 2.
8
Chiral-Zn(NTf2)2-complex-catalyzed diastereo- and enantioselective direct conjugate addition of arylacetonitriles to alkylidene malonates.手性-Zn(NTf2)2 配合物催化的芳基乙腈与亚甲基丙二酸二乙酯的立体选择性和对映选择性直接共轭加成反应。
Chemistry. 2013 Nov 25;19(48):16424-30. doi: 10.1002/chem.201302122. Epub 2013 Oct 15.
9
Total synthesis, relay synthesis, and structural confirmation of the C18-norditerpenoid alkaloid neofinaconitine.C18-降二萜生物碱新福林碱的全合成、接力合成及结构确证。
J Am Chem Soc. 2013 Sep 25;135(38):14313-20. doi: 10.1021/ja4064958. Epub 2013 Sep 16.
10
Total synthesis of cyanthiwigins A, C, G, and H.苍珊瑚素 A、C、G 和 H 的全合成。
Org Lett. 2013 Sep 6;15(17):4402-5. doi: 10.1021/ol4019425. Epub 2013 Aug 15.
Zotero 插件