手性路易斯碱催化的烯烃的硫烯氨基化反应。
Enantioselective, Lewis Base-Catalyzed, Intermolecular Sulfenoamination of Alkenes.
机构信息
Roger Adams Laboratory, Department of Chemistry , University of Illinois , Urbana , Illinois 61801 , United States.
出版信息
J Am Chem Soc. 2019 Sep 4;141(35):13767-13771. doi: 10.1021/jacs.9b07019. Epub 2019 Aug 21.
Abstract
A method for the catalytic, enantioselective, intermolecular, 1,2-sulfenoamination of alkenes is described. Functionalization is achieved through the intermediacy of an enantioenriched, configurationally stable thiiranium ion generated by Lewis base activation of a readily available sulfur electrophile. A diverse set of anilines and benzylamines react with different styrenes to afford products in good yield and stereoselectivity. Downstream manipulation of the products is facilitated by deprotonation of the amines to enable carbon-sulfur bond cleavage.
摘要
描述了一种用于催化、对映选择性、分子间 1,2-亚磺酰胺化烯烃的方法。官能化是通过路易斯碱活化易得的硫亲电试剂生成的手性富集、构型稳定的硫𬭩离子中间体实现的。各种苯胺和苄胺与不同的苯乙烯反应，以良好的收率和立体选择性得到产物。通过对胺进行脱质子化，使碳-硫键断裂，从而方便了产物的下游操作。
相似文献
1
Enantioselective, Lewis Base-Catalyzed, Intermolecular Sulfenoamination of Alkenes.手性路易斯碱催化的烯烃的硫烯氨基化反应。
J Am Chem Soc. 2019 Sep 4;141(35):13767-13771. doi: 10.1021/jacs.9b07019. Epub 2019 Aug 21.
2
Synthesis of Enantioenriched 3,4-Disubstituted Chromans through Lewis Base Catalyzed Carbosulfenylation.通过路易斯碱催化的碳硫酯化反应合成对映富集的 3,4-二取代色满
J Org Chem. 2021 Nov 5;86(21):14290-14310. doi: 10.1021/acs.joc.1c02290. Epub 2021 Oct 21.
3
Lewis Base Catalyzed, Sulfenium Ion Initiated Enantioselective, Spiroketalization Cascade.Lewis 碱催化、亚磺酰叶立德引发的对映选择性螺缩酮化级联反应。
J Org Chem. 2021 Nov 5;86(21):14250-14289. doi: 10.1021/acs.joc.1c02271. Epub 2021 Oct 21.
4
Catalytic, Enantioselective, Intramolecular Sulfenoamination of Alkenes with Anilines.烯烃与苯胺的催化、对映选择性、分子内亚磺酰胺化反应。
J Org Chem. 2017 Apr 7;82(7):3826-3843. doi: 10.1021/acs.joc.7b00391. Epub 2017 Mar 15.
5
Enantioselective Synthesis of γ-Lactams by Lewis Base Catalyzed Sulfenoamidation of Alkenes.手性 γ-内酰胺的路易斯碱催化烯基硫代酰胺化反应合成。
Org Lett. 2020 Apr 3;22(7):2501-2505. doi: 10.1021/acs.orglett.9b04347. Epub 2019 Dec 20.
6
Catalytic, Enantioselective Sulfenofunctionalization of Alkenes: Development and Recent Advances.烯烃的催化、对映选择性亚磺酰基官能化：发展与最新进展。
Angew Chem Int Ed Engl. 2020 Nov 2;59(45):19796-19819. doi: 10.1002/anie.202005920. Epub 2020 Aug 18.
7
Enantioselective Intermolecular Aminoalkynylation of Styrenes via Copper-Catalyzed Radical Relay.铜催化自由基接力实现苯乙烯的对映选择性分子间氨基炔基化反应。
Org Lett. 2021 Jan 1;23(1):129-134. doi: 10.1021/acs.orglett.0c03826. Epub 2020 Dec 16.
8
Enantioselective Inter- and Intramolecular Sulfenofunctionalization of Unactivated Cyclic and ()-Alkenes.未活化环烯烃和（）-烯烃的对映选择性分子间及分子内硫代官能化反应
ACS Catal. 2022 Jun 17;12(12):7377-7385. doi: 10.1021/acscatal.2c01232. Epub 2022 Jun 7.
9
Structural, Mechanistic, Spectroscopic, and Preparative Studies on the Lewis Base Catalyzed, Enantioselective Sulfenofunctionalization of Alkenes.关于路易斯碱催化的烯烃对映选择性亚磺酰官能化反应的结构、机理、光谱及制备研究
Helv Chim Acta. 2017 Sep;100(9). doi: 10.1002/hlca.201700158. Epub 2017 Sep 14.
10
Copper-Catalyzed Radical Relay for Asymmetric Radical Transformations.铜催化的自由基接力用于不对称自由基转化
Acc Chem Res. 2018 Sep 18;51(9):2036-2046. doi: 10.1021/acs.accounts.8b00265. Epub 2018 Sep 5.
引用本文的文献
1
Enantioselective synthesis of inherently chiral sulfur-containing calix[4]arenes via chiral sulfide catalyzed desymmetrizing aromatic sulfenylation.通过手性硫化物催化的去对称芳基亚磺酰化反应对固有手性含硫杯[4]芳烃进行对映选择性合成。
Nat Commun. 2024 Nov 15;15(1):9929. doi: 10.1038/s41467-024-54380-1.
2
Harnessing Bromo/Acyloxy Transposition (BrAcT) and Excited-State Copper Catalysis for Styrene Difunctionalization.利用溴代/酰氧基转位反应（BrAcT）和激发态铜催化实现苯乙烯的双官能化反应。
J Am Chem Soc. 2024 Aug 7;146(31):21271-21279. doi: 10.1021/jacs.4c08984. Epub 2024 Jul 23.
3
Difunctionalization Processes Enabled by Hexafluoroisopropanol.六氟异丙醇促进的双官能化反应
ACS Org Inorg Au. 2024 Mar 4;4(3):287-300. doi: 10.1021/acsorginorgau.3c00067. eCollection 2024 Jun 5.
4
Enantioselective Inter- and Intramolecular Sulfenofunctionalization of Unactivated Cyclic and ()-Alkenes.未活化环烯烃和（）-烯烃的对映选择性分子间及分子内硫代官能化反应
ACS Catal. 2022 Jun 17;12(12):7377-7385. doi: 10.1021/acscatal.2c01232. Epub 2022 Jun 7.
5
Heterocyclization of Bis(2-chloroprop-2-en-1-yl)sulfide in Hydrazine Hydrate-KOH: Synthesis of Thiophene and Pyrrole Derivatives.在水合肼-KOH 中双(2-氯丙烯-1-基)二硫醚的杂环化：噻吩和吡咯衍生物的合成。
Molecules. 2022 Oct 11;27(20):6785. doi: 10.3390/molecules27206785.
6
Directed, nickel-catalyzed 1,2-alkylsulfenylation of alkenyl carbonyl compounds.导向的镍催化烯基羰基化合物的1,2-烷基硫醚化反应。
Chem Sci. 2022 May 2;13(22):6567-6572. doi: 10.1039/d2sc01563c. eCollection 2022 Jun 7.
7
Metal-free synthesis of 1,4-benzodiazepines and quinazolinones from hexafluoroisopropyl 2-aminobenzoates at room temperature.室温下由六氟异丙基 2-氨基苯甲酸酯无金属合成 1,4-苯并二氮杂卓和喹唑啉酮。
RSC Adv. 2021 Jan 28;11(9):4966-4970. doi: 10.1039/d1ra00324k. eCollection 2021 Jan 25.
8
Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis.质子耦合电子转移在有机合成中的光化学和电化学应用。
Chem Rev. 2022 Jan 26;122(2):2017-2291. doi: 10.1021/acs.chemrev.1c00374. Epub 2021 Nov 23.
9
Ritter-enabled catalytic asymmetric chloroamidation of olefins.基于 Ritter 反应的烯烃催化不对称氯酰胺化反应。
Chem Sci. 2020 Dec 7;12(5):1834-1842. doi: 10.1039/d0sc05224h.
10
Catalytic, Enantioselective Sulfenofunctionalization of Alkenes: Development and Recent Advances.烯烃的催化、对映选择性亚磺酰基官能化：发展与最新进展。
Angew Chem Int Ed Engl. 2020 Nov 2;59(45):19796-19819. doi: 10.1002/anie.202005920. Epub 2020 Aug 18.
本文引用的文献
1
Enantioselective, Lewis Base-Catalyzed Carbosulfenylation of Alkenylboronates by 1,2-Boronate Migration.手性路易斯碱催化烯基硼酸酯的 1,2-硼迁移对映选择性碳硫酯化反应
J Am Chem Soc. 2018 Nov 21;140(46):15621-15625. doi: 10.1021/jacs.8b10288. Epub 2018 Nov 9.
2
Electrochemical oxidative oxysulfenylation and aminosulfenylation of alkenes with hydrogen evolution.烯烃的电化学氧化氧硫基化和氨硫基化反应及析氢过程
Sci Adv. 2018 Aug 3;4(8):eaat5312. doi: 10.1126/sciadv.aat5312. eCollection 2018 Aug.
3
Catalytic Enantioselective Dihalogenation in Total Synthesis.催化对映选择性双卤化反应在全合成中的应用。
Acc Chem Res. 2018 May 15;51(5):1260-1271. doi: 10.1021/acs.accounts.8b00064. Epub 2018 Apr 17.
4
Enantioselective, Lewis Base-Catalyzed Sulfenocyclization of Polyenes.对映选择性、路易斯碱催化的多烯硫环化反应。
J Am Chem Soc. 2018 Mar 14;140(10):3569-3573. doi: 10.1021/jacs.8b01660. Epub 2018 Mar 6.
5
Structural, Mechanistic, Spectroscopic, and Preparative Studies on the Lewis Base Catalyzed, Enantioselective Sulfenofunctionalization of Alkenes.关于路易斯碱催化的烯烃对映选择性亚磺酰官能化反应的结构、机理、光谱及制备研究
Helv Chim Acta. 2017 Sep;100(9). doi: 10.1002/hlca.201700158. Epub 2017 Sep 14.
6
Catalytic, Enantioselective, Intramolecular Sulfenoamination of Alkenes with Anilines.烯烃与苯胺的催化、对映选择性、分子内亚磺酰胺化反应。
J Org Chem. 2017 Apr 7;82(7):3826-3843. doi: 10.1021/acs.joc.7b00391. Epub 2017 Mar 15.
7
Catalytic, Enantioselective, Intramolecular Sulfenofunctionalization of Alkenes with Phenols.烯烃与酚的催化、对映选择性、分子内亚磺酰化反应。
J Org Chem. 2017 Mar 17;82(6):3192-3222. doi: 10.1021/acs.joc.7b00295. Epub 2017 Mar 3.
8
Diastereoselective Synthesis of syn-β-Lactams Using Rh-Catalyzed Reductive Mannich-Type Reaction of α,β-Unsaturated Esters.利用铑催化的α,β-不饱和酯的还原曼尼希型反应非对映选择性合成顺式-β-内酰胺。
J Org Chem. 2015 Aug 21;80(16):8398-405. doi: 10.1021/acs.joc.5b01233. Epub 2015 Aug 7.
9
Diaryl Selenide Catalyzed Vicinal Trifluoromethylthioamination of Alkenes.二芳基硒催化的烯烃邻位三氟甲硫基化反应
Org Lett. 2015 Jul 17;17(14):3620-3. doi: 10.1021/acs.orglett.5b01727. Epub 2015 Jul 9.
10
Mechanistic, crystallographic, and computational studies on the catalytic, enantioselective sulfenofunctionalization of alkenes.关于烯烃催化对映选择性亚磺酰官能化反应的机理、晶体学和计算研究。
Nat Chem. 2014 Dec;6(12):1056-64. doi: 10.1038/nchem.2109. Epub 2014 Nov 10.
Zotero 插件