使用 N-杂环卡宾的催化动态动力学拆分：高取代β-内酰胺的不对称合成。
Catalytic dynamic kinetic resolutions with N-heterocyclic carbenes: asymmetric synthesis of highly substituted β-lactones.
机构信息
Department of Chemistry, Center for Molecular Innovation and Drug Discovery, Chemistry of Life Processes Institute, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, USA.
出版信息
Angew Chem Int Ed Engl. 2012 Jul 16;51(29):7309-13. doi: 10.1002/anie.201203382. Epub 2012 Jun 14.
Abstract
New DKR type: An N-heterocyclic carbene (NHC)-catalyzed dynamic kinetic resolution of racemic α-substituted β-keto esters has been developed. This method relies on the epimerization of an NHC-enol intermediate before subsequent aldol/acylation events. Highly substituted β-lactones are produced in good yield with good to excellent selectivities (see scheme).
摘要
新型 DKR 类型：已开发出一种 N-杂环卡宾 (NHC)-催化的外消旋 α-取代 β-酮酯的动态动力学拆分。该方法依赖于 NHC-烯醇中间体的外消旋化，然后再进行羟醛/酰化反应。高度取代的 β-内酰胺以良好至优异的选择性（参见方案）高产率得到。
相似文献
1
Catalytic dynamic kinetic resolutions with N-heterocyclic carbenes: asymmetric synthesis of highly substituted β-lactones.使用 N-杂环卡宾的催化动态动力学拆分：高取代β-内酰胺的不对称合成。
Angew Chem Int Ed Engl. 2012 Jul 16;51(29):7309-13. doi: 10.1002/anie.201203382. Epub 2012 Jun 14.
2
N-heterocyclic-carbene-catalyzed asymmetric oxidative hetero-Diels-Alder reactions with simple aliphatic aldehydes.N-杂环卡宾催化的与简单脂肪醛的不对称氧化杂环狄尔斯-阿尔德反应。
Angew Chem Int Ed Engl. 2012 Dec 3;51(49):12330-3. doi: 10.1002/anie.201206490. Epub 2012 Nov 4.
3
N-heterocyclic carbene-catalyzed Ireland-Coates Claisen rearrangement: synthesis of functionalized β-lactones.N-杂环卡宾催化的 Ireland-CoatesClaisen 重排：功能化β-内酰胺的合成。
J Am Chem Soc. 2013 Jan 9;135(1):58-61. doi: 10.1021/ja310449k. Epub 2012 Dec 20.
4
Intermolecular dynamic kinetic resolution cooperatively catalyzed by an N-heterocyclic carbene and a Lewis acid.由 N-杂环卡宾和路易斯酸共同催化的分子间动力学动力学拆分。
Angew Chem Int Ed Engl. 2015 Jan 26;54(5):1629-33. doi: 10.1002/anie.201410030. Epub 2014 Nov 28.
5
N-heterocyclic carbene catalyzed enantioselective α-fluorination of aliphatic aldehydes and α-chloro aldehydes: synthesis of α-fluoro esters, amides, and thioesters.N-杂环卡宾催化的脂肪醛和α-氯醛的对映选择性α-氟化反应：α-氟酯、酰胺和硫酯的合成。
Angew Chem Int Ed Engl. 2015 Jan 7;54(2):660-3. doi: 10.1002/anie.201409961. Epub 2014 Nov 13.
6
Enantioselective N-heterocyclic carbene-catalyzed synthesis of indenopyrones.对映选择性 N-杂环卡宾催化的茚并吡喃酮合成
Org Biomol Chem. 2015 Jun 28;13(24):6694-7. doi: 10.1039/c5ob00859j.
7
N-heterocyclic carbene catalyzed [4+3] annulation of enals and o-quinone methides: highly enantioselective synthesis of benzo-ε-lactones.N-杂环卡宾催化烯醛与邻醌甲基化物的[4+3]环化反应：苯并-ε-内酯的高对映选择性合成
Angew Chem Int Ed Engl. 2013 Aug 12;52(33):8607-10. doi: 10.1002/anie.201303903. Epub 2013 Jul 1.
8
Enantioselective N-heterocyclic carbene catalyzed annulation reactions with imidazolidinones.手性 N-杂环卡宾催化的与咪唑烷酮的环加成反应。
Angew Chem Int Ed Engl. 2013 Dec 16;52(51):13616-20. doi: 10.1002/anie.201307292. Epub 2013 Nov 18.
9
Chiral N-heterocyclic carbene catalyzed, enantioselective oxodiene Diels-Alder reactions with low catalyst loadings.手性 N-杂环卡宾催化的、低催化剂负载量的对映选择性氧代二烯 Diels-Alder 反应。
J Am Chem Soc. 2006 Nov 29;128(47):15088-9. doi: 10.1021/ja066380r.
10
Designing N-heterocyclic carbenes: simultaneous enhancement of reactivity and enantioselectivity in the asymmetric hydroacylation of cyclopropenes.设计 N-杂环卡宾：在不对称环丙叉环丙烷的加氢甲酰化反应中同时提高反应活性和对映选择性。
Angew Chem Int Ed Engl. 2011 Dec 23;50(52):12626-30. doi: 10.1002/anie.201106155. Epub 2011 Nov 4.
引用本文的文献
1
Enantioconvergent -Pictet-Spengler Reactions: Organocatalytic Synthesis of Chiral Tetrahydro-γ-carbolines.对映汇聚式-皮克特-施彭格勒反应：手性四氢-γ-咔啉的有机催化合成
Org Lett. 2023 Jul 21;25(28):5248-5252. doi: 10.1021/acs.orglett.3c01723. Epub 2023 Jul 6.
2
Catalytic, Asymmetric Michael-Aldol Annulations via a Stereodivergent/Stereoconvergent Path Operating under Curtin-Hammett Control.通过受 Curtin-Hammett 控制的立体发散/立体协同途径进行的催化不对称迈克尔-羟醛缩合反应。
J Am Chem Soc. 2023 Jun 7;145(22):12370-12376. doi: 10.1021/jacs.3c03373. Epub 2023 May 22.
3
Dynamic kinetic resolution of γ,γ-disubstituted indole 2-carboxaldehydes NHC-Lewis acid cooperative catalysis for the synthesis of tetracyclic ε-lactones.γ,γ-二取代吲哚-2-甲醛的动态动力学拆分：用于合成四环ε-内酯的NHC-路易斯酸协同催化
Chem Sci. 2022 Aug 29;13(39):11513-11518. doi: 10.1039/d2sc03745a. eCollection 2022 Oct 12.
4
Stereodivergent Nucleophilic Additions to Racemic β-Oxo Acid Derivatives: Fast Addition Outcompetes Stereoconvergence in the Archetypal Configurationally Unstable Electrophile.对映体β-氧代酸衍生物的立体发散性亲核加成：快速加成在外消旋构型不稳定的亲电体的典型构象中胜过立体收敛。
J Am Chem Soc. 2021 Oct 6;143(39):16264-16273. doi: 10.1021/jacs.1c07702. Epub 2021 Sep 27.
5
Stereoconvergent Conjugate Addition of Arylboronic Acids to Angelica Lactone Derivatives: Synthesis of Stereochemically Complex Butyrolactones.芳基硼酸与当归内酯衍生物的立体收敛共轭加成反应：立体化学复杂的丁内酯的合成。
ACS Catal. 2019 Dec 6;9(12):11614-11618. doi: 10.1021/acscatal.9b04405. Epub 2019 Nov 19.
6
-Heterocyclic carbene catalysed redox isomerisation of esters to functionalised benzaldehydes.- 杂环卡宾催化酯向官能化苯甲醛的氧化还原异构化反应。
Chem Sci. 2015 Apr 1;6(4):2366-2370. doi: 10.1039/c4sc03726j. Epub 2015 Jan 26.
7
Synthesis of Complex Glycolates by Enantioconvergent Addition Reactions.通过对映选择性加成反应合成复杂的醇酸盐。
Acc Chem Res. 2017 Sep 19;50(9):2284-2296. doi: 10.1021/acs.accounts.7b00263. Epub 2017 Aug 17.
8
Direct Zinc(II)-Catalyzed Enantioconvergent Additions of Terminal Alkynes to α-Keto Esters.直接锌(II)催化的末端炔烃对α-酮酯的对映转化加成反应。
Angew Chem Int Ed Engl. 2017 Jul 17;56(30):8805-8808. doi: 10.1002/anie.201704226. Epub 2017 Jun 20.
9
Synthesis of Complex Tertiary Glycolates by Enantioconvergent Arylation of Stereochemically Labile α-Keto Esters.通过对立体化学不稳定的α-酮酯的对映选择性芳基化反应合成复杂的叔醇盐。
J Am Chem Soc. 2017 Mar 15;139(10):3911-3916. doi: 10.1021/jacs.7b00943. Epub 2017 Mar 2.
10
Enantioconvergent catalysis.对映汇聚催化
Beilstein J Org Chem. 2016 Sep 16;12:2038-2045. doi: 10.3762/bjoc.12.192. eCollection 2016.
本文引用的文献
1
An N-heterocyclic carbene/Lewis acid strategy for the stereoselective synthesis of spirooxindole lactones.N-杂环卡宾/路易斯酸策略用于立体选择性合成螺[吲哚啉-2,3’-吡咯烷]-2,5-二酮。
Angew Chem Int Ed Engl. 2012 May 14;51(20):4963-7. doi: 10.1002/anie.201201643. Epub 2012 Apr 4.
2
Asymmetric spiroacetalization catalysed by confined Brønsted acids.受限 Brønsted 酸催化的不对称螺缩酮化反应。
Nature. 2012 Mar 14;483(7389):315-9. doi: 10.1038/nature10932.
3
Protonation of Homoenolate Equivalents Generated by N-Heterocyclic Carbenes.由氮杂环卡宾生成的高烯醇负离子类似物的质子化反应。
Synthesis (Stuttg). 2008 Apr;2008(8):1306-1315. doi: 10.1055/s-2008-1072516.
4
Chiral silver phosphate-catalyzed cycloisomeric kinetic resolution of α-allenic alcohols.手性磷酸银催化的 α-烯丙醇的环异构动力学拆分。
J Am Chem Soc. 2012 Mar 7;134(9):4096-9. doi: 10.1021/ja300453u. Epub 2012 Feb 27.
5
A diastereoselective, nucleophile-promoted aldol-lactonization of ketoacids leading to bicyclic-β-lactones.一种非对映选择性的、亲核试剂促进的酮酸的Aldol-内酯化反应，生成双环-β-内酰胺。
J Org Chem. 2012 Mar 2;77(5):2496-500. doi: 10.1021/jo202252y. Epub 2012 Feb 14.
6
Amidines, isothioureas, and guanidines as nucleophilic catalysts.脒类、异硫脲和胍类作为亲核催化剂。
Chem Soc Rev. 2012 Mar 21;41(6):2109-21. doi: 10.1039/c2cs15288f. Epub 2012 Jan 10.
7
Catalytic kinetic resolution of cyclic secondary amines.催化动力学拆分环状仲胺。
J Am Chem Soc. 2011 Dec 14;133(49):19698-701. doi: 10.1021/ja209472h. Epub 2011 Nov 18.
8
The catalytic asymmetric Fischer indolization.催化不对称 Fischer 吲哚化反应。
J Am Chem Soc. 2011 Nov 23;133(46):18534-7. doi: 10.1021/ja2092163. Epub 2011 Nov 1.
9
Enamine/Carbene Cascade Catalysis in the Diastereo- and Enantioselective Synthesis of Functionalized Cyclopentanones.烯胺/卡宾串联催化用于功能化环戊酮的非对映和对映选择性合成
Chem Sci. 2011 Sep 1;2(9):1835-1838. doi: 10.1039/C1SC00175B.
10
Understanding the cooperative NHC/LA catalysis for stereoselective annulation reactions with homoenolates. A DFT study.理解 NHC/LA 协同催化的高烯醇酯立体选择性环化反应。DFT 研究。
Org Biomol Chem. 2011 Oct 7;9(19):6616-22. doi: 10.1039/c1ob05609c. Epub 2011 Aug 15.
Zotero 插件