通过铜催化的酚对 N-磺酰基亚胺的对映选择性氮杂 Friedel-Crafts 加成反应合成苄基胺。
Synthesis of Benzyl Amines via Copper-Catalyzed Enantioselective Aza-Friedel-Crafts Addition of Phenols to N-Sulfonyl Aldimines.
机构信息
Chemistry Department, Natural Science Complex , State University of New York at Buffalo , Buffalo , New York 14260 , United States.
出版信息
Org Lett. 2018 Apr 20;20(8):2133-2137. doi: 10.1021/acs.orglett.8b00282. Epub 2018 Mar 28.
Abstract
A new copper-catalyzed enantioselective aza-Freidel-Crafts reaction between phenols and N-sulfonyl aldimines that provides chiral secondary benzylamines in good to excellent yields and excellent enantioselectivities (up to 99% ee) is disclosed. In particular, excellent scope with alkylimines was observed for the first time. The synthetic utility of the products was demonstrated in the first enantioselective synthesis of a dual orexin receptor antagonist, a compound that contains an amine-bearing stereocenter adjacent to a bis- ortho-functionalized arene.
摘要
本文报道了一种新型的铜催化的酚和 N-磺酰基亚胺之间的对映选择性氮杂弗里德尔-克拉夫茨反应，该反应以良好到优秀的收率和优异的对映选择性（高达 99%ee）提供了手性仲苄胺。特别是，首次观察到烷基亚胺具有优异的适用范围。产物的合成实用性在首例双食欲素受体拮抗剂的对映选择性合成中得到了证明，该化合物含有一个胺基手性中心，紧邻双邻位官能化芳烃。
相似文献
1
Synthesis of Benzyl Amines via Copper-Catalyzed Enantioselective Aza-Friedel-Crafts Addition of Phenols to N-Sulfonyl Aldimines.通过铜催化的酚对 N-磺酰基亚胺的对映选择性氮杂 Friedel-Crafts 加成反应合成苄基胺。
Org Lett. 2018 Apr 20;20(8):2133-2137. doi: 10.1021/acs.orglett.8b00282. Epub 2018 Mar 28.
2
A copper(II)-catalyzed aza-Friedel-Crafts reaction of N-(2-pyridyl)sulfonyl aldimines: synthesis of unsymmetrical diaryl amines and triaryl methanes.铜（II）催化的N-（2-吡啶基）磺酰基亚胺的氮杂傅克反应：不对称二芳基胺和三芳基甲烷的合成
Angew Chem Int Ed Engl. 2006 Jan 16;45(4):629-33. doi: 10.1002/anie.200503305.
3
Chiral phosphoric acid-catalyzed enantioselective aza-Friedel-Crafts reaction of naphthols and electron-rich phenols with 2-aryl-3-indol-3-ones.手性磷酸催化萘酚和富电子酚与2-芳基-3-吲哚-3-酮的对映选择性氮杂傅克反应。
Org Biomol Chem. 2023 Jan 18;21(3):489-493. doi: 10.1039/d2ob02179j.
4
5
N,N'-dioxide-scandium(III)-catalyzed asymmetric Aza-Friedel-Crafts reaction of sesamol with aldimines.N,N'-二氧化物-钪(III)催化芝麻酚与醛亚胺的不对称氮杂傅-克反应
J Org Chem. 2014 Nov 7;79(21):10662-8. doi: 10.1021/jo5020036. Epub 2014 Oct 29.
6
Enantioselective Friedel-Crafts reactions between phenols and N-tosylaldimines catalyzed by a leucine-derived bifunctional catalyst.手性双功能催化剂催化的酚与 N-对甲苯磺酰亚胺的不对称傅克反应。
Chem Commun (Camb). 2012 Jun 4;48(44):5518-20. doi: 10.1039/c2cc31735d. Epub 2012 Apr 27.
7
H₈-BINOL chiral imidodiphosphoric acid catalyzed highly enantioselective aza-Friedel-Crafts reactions of pyrroles and enamides/imines.H₈-联萘酚手性亚氨基二磷酸催化吡咯与烯酰胺/亚胺的高对映选择性氮杂傅克反应。
Chem Commun (Camb). 2015 May 11;51(38):8054-7. doi: 10.1039/c5cc00685f. Epub 2015 Apr 13.
8
Aymmetric Aza-Friedel-Crafts Reaction of Isatin-Derived Ketimines with Indoles Catalyzed by a Chiral Phase-Transfer Catalyst.手性相转移催化剂催化的异吲哚酮衍生酮亚胺与吲哚的不对称氮杂傅克反应
J Org Chem. 2022 Mar 4;87(5):2532-2542. doi: 10.1021/acs.joc.1c02477. Epub 2022 Jan 27.
9
Enantioselective synthesis of cyclic quaternary α-amino acid derivatives by chiral phosphoric acid catalysis.通过手性磷酸催化对环状季铵α-氨基酸衍生物进行对映选择性合成。
Org Biomol Chem. 2017 Jul 19;15(28):6033-6041. doi: 10.1039/c7ob01149k.
10
Enantioselective conjugate addition of both aromatic ketones and acetone to nitroolefins catalyzed by chiral primary amines bearing multiple hydrogen-bonding donors.手性伯胺多氢键给体催化芳香酮和丙酮与硝基烯烃的对映选择性共轭加成。
J Org Chem. 2012 Apr 20;77(8):4103-10. doi: 10.1021/jo300011x. Epub 2012 Mar 29.
引用本文的文献
1
Further Developments and Applications of Oxazoline-Containing Ligands in Asymmetric Catalysis.含恶唑啉配体在不对称催化中的进一步发展与应用。
Chem Rev. 2021 Jun 9;121(11):6373-6521. doi: 10.1021/acs.chemrev.0c00844. Epub 2021 May 21.
2
Synthesis of Benzylureas and Related Amine Derivatives via Copper-Catalyzed Three-Component Carboamination of Styrenes.通过铜催化的苯乙烯三组分碳氨化反应合成苯甲酰脲及相关胺衍生物。
Org Lett. 2020 Nov 6;22(21):8365-8369. doi: 10.1021/acs.orglett.0c02988. Epub 2020 Oct 19.
3
A Revised Modular Approach to (-)--Δ-THC and Derivatives Through Late-Stage Suzuki-Miyaura Cross-Coupling Reactions.一种通过后期铃木-宫浦交叉偶联反应合成(-)--Δ-四氢大麻酚及其衍生物的改进模块化方法。
European J Org Chem. 2019 Mar 31;2019(12):2289-2296. doi: 10.1002/ejoc.201900059. Epub 2019 Mar 18.
4
Delayed catalyst function enables direct enantioselective conversion of nitriles to NH-amines.延迟的催化剂功能能够实现腈直接对映选择性转化为NH-胺。
Science. 2019 Apr 5;364(6435):45-51. doi: 10.1126/science.aaw4029.
本文引用的文献
1
An Arylation Strategy to Propargylamines: Catalytic Asymmetric Friedel-Crafts-type Arylation Reactions of C-Alkynyl Imines.芳基化策略的炔丙胺：C-炔基亚胺的催化不对称傅克型芳基化反应。
Angew Chem Int Ed Engl. 2016 Nov 21;55(48):15142-15146. doi: 10.1002/anie.201608918. Epub 2016 Oct 27.
2
Synthesis of 1,4-amino alcohols by Grignard reagent addition to THF and N-tosyliminobenzyliodinane.通过格氏试剂加成到四氢呋喃和N-对甲苯磺酰基亚胺苄碘烷合成1,4-氨基醇。
Org Biomol Chem. 2016 Jan 21;14(3):844-8. doi: 10.1039/c5ob02302e. Epub 2015 Dec 2.
3
Entropy-Driven 1,2-Type Friedel-Crafts Reaction of Phenols with N-tert-Butoxycarbonyl Aldimines.酚与N-叔丁氧羰基醛亚胺的熵驱动1,2-型傅克反应
Chemistry. 2015 Dec 14;21(51):18606-12. doi: 10.1002/chem.201503280. Epub 2015 Nov 6.
4
A Quinine-Squaramide Catalyzed Enantioselective Aza-Friedel-Crafts Reaction of Cyclic Trifluoromethyl Ketimines with Naphthols and Electron-Rich Phenols.奎宁-磺胺酰胺催化的手性环三氟甲基亚胺与萘酚和富电子苯酚的aza-Friedel-Crafts 反应。
Org Lett. 2015 Nov 20;17(22):5554-7. doi: 10.1021/acs.orglett.5b02668. Epub 2015 Nov 2.
5
Organocatalytic asymmetric addition of naphthols and electron-rich phenols to isatin-derived ketimines: highly enantioselective construction of tetrasubstituted stereocenters.有机催化的萘酚和富电子苯酚与色酮衍生的亚胺的不对称加成：高对映选择性构建四取代立体中心。
Angew Chem Int Ed Engl. 2015 May 18;54(21):6320-4. doi: 10.1002/anie.201501273. Epub 2015 Apr 2.
6
Substituted pyrrolidin-2-ones: Centrally acting orexin receptor antagonists promoting sleep. Part 2.取代吡咯烷-2-酮：中枢作用的食欲素受体拮抗剂促进睡眠。第2部分。
Bioorg Med Chem Lett. 2015 May 1;25(9):1884-91. doi: 10.1016/j.bmcl.2015.03.035. Epub 2015 Mar 21.
7
N,N'-dioxide-scandium(III)-catalyzed asymmetric Aza-Friedel-Crafts reaction of sesamol with aldimines.N,N'-二氧化物-钪(III)催化芝麻酚与醛亚胺的不对称氮杂傅-克反应
J Org Chem. 2014 Nov 7;79(21):10662-8. doi: 10.1021/jo5020036. Epub 2014 Oct 29.
8
C3-Symmetric chiral trisimidazoline-catalyzed Friedel-Crafts (FC)-type reaction.C3对称手性三咪唑啉催化的傅克（FC）型反应。
Org Biomol Chem. 2014 Aug 21;12(31):5827-30. doi: 10.1039/c4ob00925h.
9
Discovery of substituted lactams as novel dual orexin receptor antagonists. Synthesis, preliminary structure-activity relationship studies and efforts towards improved metabolic stability and pharmacokinetic properties. Part 1.发现取代的内酰胺类化合物作为新型双重食欲素受体拮抗剂。合成、初步的构效关系研究以及改善代谢稳定性和药代动力学性质的努力。第 1 部分。
Bioorg Med Chem Lett. 2014 Feb 15;24(4):1201-8. doi: 10.1016/j.bmcl.2013.12.092. Epub 2013 Dec 30.
10
Discovery of a novel small molecule inhibitor targeting the frataxin/ubiquitin interaction via structure-based virtual screening and bioassays.通过基于结构的虚拟筛选和生物测定发现靶向 frataxin/泛素相互作用的新型小分子抑制剂。
J Med Chem. 2013 Apr 11;56(7):2861-73. doi: 10.1021/jm3017199. Epub 2013 Mar 29.
Zotero 插件