高碱性烯醇盐与邻醌甲基化物的迈克尔加成反应
Michael Additions of Highly Basic Enolates to ortho-Quinone Methides.
作者信息
Lewis Robert S, Garza Christopher J, Dang Ann T, Pedro Te Kie A, Chain William J
机构信息
†Department of Chemistry, University of Hawaii at Manoa, 2545 McCarthy Mall, Honolulu, Hawaii 96822, United States.
‡The University of Hawaii Cancer Center, 701 Ilalo Street, Honolulu, Hawaii 96813, United States.
出版信息
Org Lett. 2015 May 1;17(9):2278-81. doi: 10.1021/acs.orglett.5b00972. Epub 2015 Apr 23.
Abstract
A protocol by which ketone or ester enolates and ortho-quinone methides (o-QMs) are generated in situ in a single reaction flask from silylated precursors under the action of anhydrous fluoride is reported. The reaction partners are joined to give a variety of β-(2-hydroxyphenyl)-carbonyl compounds in 32-94% yield in a single laboratory operation. The intermediacy of o-QMs is supported by control experiments utilizing enolate precursors and conventional alkyl halides as competitive alkylating agents and the isolation of 1,5-dicarbonyl products resulting from conjugate additions that do not restore the aromatic system.
摘要
报道了一种在无水氟化物作用下，从硅烷基化前体在单个反应烧瓶中原位生成酮或酯烯醇盐和邻醌甲基化物（o-QMs）的方案。在单一实验室操作中，反应伙伴结合生成各种β-(2-羟基苯基)-羰基化合物，产率为32-94%。利用烯醇盐前体和传统卤代烷作为竞争性烷基化剂的对照实验以及未恢复芳环体系的共轭加成产生的1,5-二羰基产物的分离，支持了o-QMs的中间体性质。
相似文献
1
Michael Additions of Highly Basic Enolates to ortho-Quinone Methides.高碱性烯醇盐与邻醌甲基化物的迈克尔加成反应
Org Lett. 2015 May 1;17(9):2278-81. doi: 10.1021/acs.orglett.5b00972. Epub 2015 Apr 23.
2
Enantio- and diastereoselective access to distant stereocenters embedded within tetrahydroxanthenes: utilizing ortho-quinone methides as reactive intermediates in asymmetric Brønsted acid catalysis.对映选择性和非对映选择性地构建四氢蒽酮中远程手性中心：利用邻醌甲醚作为不对称布朗斯特酸催化中的反应中间体。
Angew Chem Int Ed Engl. 2014 Nov 24;53(48):13258-63. doi: 10.1002/anie.201406587. Epub 2014 Oct 6.
3
Substrate-controlled Michael additions of chiral ketones to enones.手性酮对烯酮的底物控制的迈克尔加成反应。
Org Lett. 2014 Dec 5;16(23):6220-3. doi: 10.1021/ol503133j. Epub 2014 Nov 25.
4
Asymmetric cycloadditions of o-quinone methides employing chiral ammonium fluoride precatalysts.使用手性氟化铵预催化剂的邻醌甲基化物的不对称环加成反应。
Org Lett. 2008 Nov 6;10(21):4951-3. doi: 10.1021/ol802029e. Epub 2008 Oct 14.
5
Catalytic Asymmetric 1,6-Conjugate Addition of para-Quinone Methides: Formation of All-Carbon Quaternary Stereocenters.对醌甲基化物的催化不对称 1,6-共轭加成：全碳季碳中心的形成。
Angew Chem Int Ed Engl. 2015 Nov 9;54(46):13711-4. doi: 10.1002/anie.201506701. Epub 2015 Sep 25.
6
Diastereoselective syntheses of chroman spiroketals via [4 + 2] cycloaddition of enol ethers and o-quinone methides.通过烯醇醚与邻醌甲基化物的[4 + 2]环加成反应实现色满螺缩酮的非对映选择性合成。
Org Lett. 2008 Apr 3;10(7):1477-80. doi: 10.1021/ol8003244. Epub 2008 Mar 13.
7
[4 + 2]-Cycloaddition and 1,4-Addition of ortho-Quinone Methides by a Chiral Crotyl Silane.[4 + 2]-环加成和邻醌甲醚的 1,4-加成反应由手性烯丙基硅烷引发。
Org Lett. 2019 Jan 4;21(1):32-35. doi: 10.1021/acs.orglett.8b03395. Epub 2018 Dec 17.
8
The domestication of ortho-quinone methides.邻醌甲基化物的驯化
Acc Chem Res. 2014 Dec 16;47(12):3655-64. doi: 10.1021/ar500330x. Epub 2014 Dec 3.
9
o-Quinone Methides via Oxone-Mediated Benzofuran Oxidative Dearomatization and Their Intramolecular Cycloaddition with Carbonyl Groups: An Expeditious Construction of the Central Tetracyclic Core of Integrastatins, Epicoccolide A, and Epicocconigrone A.通过过氧单磺酸钾介导的苯并呋喃氧化脱芳构化反应制备邻醌甲基化物及其与羰基的分子内环加成反应：快速构建整合素抑制剂、表棒曲霉素A和表棒曲霉素A的中心四环核心结构
Org Lett. 2016 Feb 5;18(3):612-5. doi: 10.1021/acs.orglett.5b03707. Epub 2016 Jan 27.
10
Pyridin-2-one synthesis using ester enolates and aryl aminoaldehydes and ketones.使用酯烯醇盐与芳基氨基醛和酮合成吡啶-2-酮。
J Org Chem. 2014 Apr 4;79(7):3260-6. doi: 10.1021/jo500284n. Epub 2014 Mar 24.
引用本文的文献
1
Enantioselective Total Synthesis of (-)-Psiguadial A.(-)-Psiguadial A的对映选择性全合成。
Angew Chem Int Ed Engl. 2025 Jul 21;64(30):e202506537. doi: 10.1002/anie.202506537. Epub 2025 May 26.
2
Synthesis of Functionalized Tetrahydroquinoline Containing Indole Scaffold via Chemoselective Annulation of Aza--quinone Methide Precursor.通过氮杂-醌甲基化物前体的化学选择性环化合成含吲哚骨架的功能化四氢喹啉
ACS Omega. 2023 Jun 13;8(25):22352-22360. doi: 10.1021/acsomega.2c07036. eCollection 2023 Jun 27.
3
Recent Developments with Icetexane Natural Products.Icetexane 天然产物的最新进展。
Chem Biodivers. 2022 Nov;19(11):e202200793. doi: 10.1002/cbdv.202200793. Epub 2022 Nov 8.
4
Synthesis, Biological Evaluation, and Docking Studies of Antagonistic Hydroxylated Arecaidine Esters Targeting mAChRs.合成、生物评价及靶向 mAChRs 的羟基化槟榔碱酯的对接研究。
Molecules. 2022 May 16;27(10):3173. doi: 10.3390/molecules27103173.
5
3-Heterosubstituted Benzofurans from Hydroxyphenyl Propargyl Alcohols via -Quinone Methide through a Metal-/Catalyst-Free Conjugate Addition/Oxy-Cyclization.通过对苯醌甲基化物，由羟基苯基炔丙醇经无金属/无催化剂的共轭加成/氧环化反应合成3-杂取代苯并呋喃。
ACS Omega. 2018 Dec 12;3(12):17155-17163. doi: 10.1021/acsomega.8b02480. eCollection 2018 Dec 31.
6
A Strategy toward Icetexane Natural Products.一种针对冰叶烷天然产物的策略。
European J Org Chem. 2018 Jul 6;2018(25):3348-3351. doi: 10.1002/ejoc.201800707. Epub 2018 May 16.
7
Synthesis and post-functionalization of alternate-linked-[2 .1 ]thiacyclophanes.交替连接的-[2.1]硫杂环番的合成与后功能化
Beilstein J Org Chem. 2018 Aug 22;14:2190-2197. doi: 10.3762/bjoc.14.192. eCollection 2018.
8
Transformation of N, N-Dimethylaniline N-Oxides into Diverse Tetrahydroquinoline Scaffolds via Formal Povarov Reactions.N,N-二甲基苯胺 N-氧化物通过形式 Povarov 反应转化为多样的四氢喹啉骨架。
Org Lett. 2018 Sep 7;20(17):5406-5409. doi: 10.1021/acs.orglett.8b02318. Epub 2018 Aug 15.
本文引用的文献
1
The domestication of ortho-quinone methides.邻醌甲基化物的驯化
Acc Chem Res. 2014 Dec 16;47(12):3655-64. doi: 10.1021/ar500330x. Epub 2014 Dec 3.
2
Enantioselective annulations for dihydroquinolones by in situ generation of azolium enolates.通过原位生成唑鎓烯醇盐实现二氢喹诺酮的对映选择性环化反应。
J Am Chem Soc. 2014 Jul 30;136(30):10589-92. doi: 10.1021/ja505880r. Epub 2014 Jul 15.
3
Brønsted acid catalyzed, conjugate addition of β-dicarbonyls to in situ generated ortho-quinone methides--enantioselective synthesis of 4-aryl-4H-chromenes.布朗斯特酸催化的β-二羰基化合物与原位生成的邻醌甲醚的共轭加成反应——4-芳基-4H-色烯的对映选择性合成。
Angew Chem Int Ed Engl. 2014 Jul 21;53(30):7923-7. doi: 10.1002/anie.201403573. Epub 2014 Jun 18.
4
Total synthesis and isolation of citrinalin and cyclopiamine congeners.全合成及 citrinalin 和 cyclopiamine 同系物的分离。
Nature. 2014 May 15;509(7500):318-324. doi: 10.1038/nature13273.
5
A dual Lewis base activation strategy for enantioselective carbene-catalyzed annulations.双路易斯碱活化策略用于手性卡宾催化的环加成反应。
J Am Chem Soc. 2013 Jul 24;135(29):10634-7. doi: 10.1021/ja405833m. Epub 2013 Jul 11.
6
Mild and rapid method for the generation of ortho-(naphtho)quinone methide intermediates.温和快速生成邻-(萘基)醌甲叉中间体的方法。
Org Lett. 2012 Jan 20;14(2):584-7. doi: 10.1021/ol203196n. Epub 2012 Jan 10.
7
Computational prediction of 1H and 13C chemical shifts: a useful tool for natural product, mechanistic, and synthetic organic chemistry.1H和13C化学位移的计算预测：天然产物、机理及合成有机化学的有用工具。
Chem Rev. 2012 Mar 14;112(3):1839-62. doi: 10.1021/cr200106v. Epub 2011 Nov 17.
8
Applications of ortho-quinone methide intermediates in catalysis and asymmetric synthesis.芳氧甲叉中间体在催化和不对称合成中的应用。
J Org Chem. 2011 Nov 18;76(22):9210-5. doi: 10.1021/jo201789k. Epub 2011 Oct 19.
9
Intermolecular Michael reactions: a computational investigation.分子间迈克尔反应的计算研究。
Org Lett. 2010 Nov 19;12(22):5124-7. doi: 10.1021/ol102017v. Epub 2010 Oct 1.
10
Asymmetric cycloadditions of o-quinone methides employing chiral ammonium fluoride precatalysts.使用手性氟化铵预催化剂的邻醌甲基化物的不对称环加成反应。
Org Lett. 2008 Nov 6;10(21):4951-3. doi: 10.1021/ol802029e. Epub 2008 Oct 14.
Zotero 插件