不对称去芳构化/环化反应助力多环化学结构类型的构建。
Asymmetric Dearomatization/Cyclization Enables Access to Polycyclic Chemotypes.
作者信息
Hayashi Mikayo, Brown Lauren E, Porco John A
机构信息
Department of Chemistry, Center for Molecular Discovery, Boston University, 590 Commonwealth Avenue, Boston, MA 02215 (USA).
Department of Chemistry, Center for Molecular Discovery, Boston University, 590 Commonwealth Avenue, Boston, MA 02215 (USA),
出版信息
European J Org Chem. 2016 Oct;2016(28):4800-4804. doi: 10.1002/ejoc.201601003.
Abstract
Enantioenriched, polycyclic compounds were obtained from a simple acylphloroglucinol scaffold. Highly enantioselective dearomatization was accomplished using a Trost ligand-palladium(0) complex. A computational DFT model was developed to rationalize observed enantioselectivities and revealed a key reactant-ligand hydrogen bonding interaction. Dearomatized products were used in visible light-mediated photocycloadditions and oxidative free radical cyclizations to obtain novel polycyclic chemotypes including tricyclo[4.3.1.0]decan-10-ones, bicyclo[3.2.1]octan-8-ones and highly-substituted cycloheptanones.
摘要
对映体富集的多环化合物是从简单的酰基间苯三酚支架中获得的。使用特罗斯特配体-钯(0)络合物实现了高度对映选择性的去芳构化反应。开发了一个计算密度泛函理论(DFT)模型来解释观察到的对映选择性，并揭示了一种关键的反应物-配体氢键相互作用。去芳构化产物用于可见光介导的光环加成反应和氧化自由基环化反应，以获得新型的多环化学类型，包括三环[4.3.1.0]癸-10-酮、双环[3.2.1]辛-8-酮和高度取代的环庚酮。
相似文献
1
Asymmetric Dearomatization/Cyclization Enables Access to Polycyclic Chemotypes.不对称去芳构化/环化反应助力多环化学结构类型的构建。
European J Org Chem. 2016 Oct;2016(28):4800-4804. doi: 10.1002/ejoc.201601003.
2
Transition-metal-catalyzed asymmetric allylic dearomatization reactions.过渡金属催化的不对称烯丙基去芳构化反应。
Acc Chem Res. 2014 Aug 19;47(8):2558-73. doi: 10.1021/ar500167f. Epub 2014 Jun 18.
3
Palladium-catalyzed asymmetric synthesis of allylic fluorides.钯催化的烯丙基氟化物的不对称合成。
J Am Chem Soc. 2010 Dec 15;132(49):17402-4. doi: 10.1021/ja109120n. Epub 2010 Nov 18.
4
Palladium(0)-Catalyzed Intermolecular Asymmetric Cascade Dearomatization Reaction of Indoles with Propargyl Carbonate.钯(0)催化吲哚与丙炔碳酸酯的分子间不对称串联去芳构化反应。
Chemistry. 2019 Mar 21;25(17):4330-4334. doi: 10.1002/chem.201900425. Epub 2019 Feb 19.
5
Construction of Various Bridged Polycyclic Skeletons by Palladium-Catalyzed Dearomatization.钯催化去芳构化构建各种桥连多环骨架。
Angew Chem Int Ed Engl. 2020 May 18;59(21):8143-8147. doi: 10.1002/anie.202000953. Epub 2020 Mar 13.
6
Enantioselective Synthesis of Pyrrole-Based Spiro- and Polycyclic Derivatives by Iridium-Catalyzed Asymmetric Allylic Dearomatization and Controllable Migration Reactions.通过铱催化不对称烯丙基去芳构化和可控迁移反应合成基于吡咯的螺环和多环衍生物的对映选择性方法。
Angew Chem Int Ed Engl. 2015 Jul 13;54(29):8475-9. doi: 10.1002/anie.201502259. Epub 2015 Jun 3.
7
Bioinspired Total Synthesis of Hyperireflexolides A and B.受生物启发的海菲莱克斯 A 和 B 的全合成。
Org Lett. 2023 Sep 1;25(34):6317-6321. doi: 10.1021/acs.orglett.3c02232. Epub 2023 Aug 22.
8
Exploration of Visible-Light Photocatalysis in Heterocycle Synthesis and Functionalization: Reaction Design and Beyond.可见光催化在杂环合成与功能化中的应用探索：反应设计及其他。
Acc Chem Res. 2016 Sep 20;49(9):1911-23. doi: 10.1021/acs.accounts.6b00254. Epub 2016 Aug 23.
9
Catalytic Enantioselective Radical Transformations Enabled by Visible Light.可见光促进的手性自由基转化反应。
Chem Asian J. 2020 Jul 16;15(14):2129-2152. doi: 10.1002/asia.202000525. Epub 2020 Jun 17.
10
Diastereo- and Enantioselective Construction of the Hexahydrocoumarin Scaffold via an Organocatalytic Asymmetric [3 + 3] Cyclization.通过有机催化不对称[3+3]环化反应构建六氢香豆素骨架的非对映选择性和对映选择性。
J Org Chem. 2016 Jun 17;81(12):5056-65. doi: 10.1021/acs.joc.6b00603. Epub 2016 Jun 1.
引用本文的文献
1
Biomimetic Synthesis of Meroterpenoids by Dearomatization-Driven Polycyclization.仿生合成通过去芳构化驱动的多环化反应的倍半萜类化合物。
Angew Chem Int Ed Engl. 2019 Nov 4;58(45):16141-16146. doi: 10.1002/anie.201910710. Epub 2019 Sep 25.
2
Regiodivergent Photocyclization of Dearomatized Acylphloroglucinols: Asymmetric Syntheses of (-)-Nemorosone and (-)-6--Garcimultiflorone A.去芳基酰基间苯三酚的区域发散光环化：(-)-新乌头宁和(-)-6--garcimultiflorone A 的不对称合成。
J Am Chem Soc. 2019 Jul 17;141(28):11315-11321. doi: 10.1021/jacs.9b05600. Epub 2019 Jul 2.
本文引用的文献
1
Photochemical Approaches to Complex Chemotypes: Applications in Natural Product Synthesis.复杂化学类型的光化学方法：在天然产物合成中的应用。
Chem Rev. 2016 Sep 14;116(17):9683-747. doi: 10.1021/acs.chemrev.5b00760. Epub 2016 Apr 27.
2
Catalytic Alkene Carboaminations Enabled by Oxidative Proton-Coupled Electron Transfer.氧化质子耦合电子转移实现的催化烯烃碳胺化反应
J Am Chem Soc. 2015 Jul 29;137(29):9226-9. doi: 10.1021/jacs.5b05377. Epub 2015 Jul 15.
3
[2+2] cycloaddition of 1,3-dienes by visible light photocatalysis.1,3 - 二烯通过可见光光催化进行的[2 + 2]环加成反应。
Angew Chem Int Ed Engl. 2014 Aug 18;53(34):8991-4. doi: 10.1002/anie.201405359. Epub 2014 Jul 1.
4
Asymmetric, stereodivergent synthesis of (-)-clusianone utilizing a biomimetic cationic cyclization.利用仿生阳离子环化反应实现（-）-clusianone的不对称、立体发散合成。
Angew Chem Int Ed Engl. 2014 Jul 21;53(30):7832-7. doi: 10.1002/anie.201404437. Epub 2014 Jun 10.
5
The total syntheses of guttiferone A and 6-epi-guttiferone A.guttiferone A 和 6-epi-guttiferone A 的全合成。
J Am Chem Soc. 2014 Mar 12;136(10):4026-30. doi: 10.1021/ja500063a. Epub 2014 Mar 3.
6
Bridgehead enolate or bridgehead organolithium? DFT calculations provide insights into a difficult bridgehead substitution reaction in the synthesis of the polycyclic polyprenylated acylphloroglucinol (PPAP) nemorosone.桥头烯醇盐或桥头有机锂？DFT 计算深入了解多环聚异戊烯基酰基间苯三酚（PPAP）化合物nemorosone 合成中桥头取代反应的难题。
Org Biomol Chem. 2013 Dec 28;11(48):8458-62. doi: 10.1039/c3ob41064a. Epub 2013 Nov 8.
7
Palladium-catalyzed intermolecular asymmetric allylic dearomatization reaction of naphthol derivatives.钯催化的萘酚衍生物的分子间不对称烯丙基去芳构化反应。
Angew Chem Int Ed Engl. 2013 Sep 16;52(38):10056-9. doi: 10.1002/anie.201304591. Epub 2013 Aug 9.
8
Enantioselective total synthesis of hyperforin.手性全合成贯叶金丝桃素。
J Am Chem Soc. 2013 Jan 16;135(2):644-7. doi: 10.1021/ja312150d. Epub 2012 Dec 31.
9
The reaction mechanism of the enantioselective Tsuji allylation: inner-sphere and outer-sphere pathways, internal rearrangements, and asymmetric C-C bond formation.对映选择性 Tsuji 烯丙基化反应的反应机理：内球和外球途径、内部重排和不对称 C-C 键形成。
J Am Chem Soc. 2012 Nov 21;134(46):19050-60. doi: 10.1021/ja306860n. Epub 2012 Nov 6.
10
Visible light photocatalysis of [2+2] styrene cycloadditions by energy transfer.可见光促进的[2+2]环加成反应的能量转移光催化。
Angew Chem Int Ed Engl. 2012 Oct 8;51(41):10329-32. doi: 10.1002/anie.201204835. Epub 2012 Sep 10.
Zotero 插件