未保护脂环胺的区域选择性α-氰化反应
Regioselective α-Cyanation of Unprotected Alicyclic Amines.
作者信息
Yu Fuchao, Valles Daniel A, Chen Weijie, Daniel Scott D, Ghiviriga Ion, Seidel Daniel
机构信息
Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, Gainesville, Florida 32611, United States.
Faculty of Life Science and Technology, Kunming University of Science and Technology, Kunming 650500, P. R. China.
出版信息
Org Lett. 2022 Sep 9;24(35):6364-6368. doi: 10.1021/acs.orglett.2c02148. Epub 2022 Aug 29.
Abstract
Secondary alicyclic amines are converted to α-aminonitriles via addition of TMSCN to their corresponding imines, intermediates that are produced in situ via the oxidation of amine-derived lithium amides with simple ketone oxidants. Amines with an existing α-substituent undergo regioselective α'-cyanation even if the C-H bonds at that site are less activated. Amine α-arylation can be combined with α'-cyanation to generate difunctionalized products in a single operation.
摘要
仲脂环胺通过将三甲基氰硅烷（TMSCN）加成到其相应的亚胺上转化为α-氨基腈，这些亚胺中间体是通过胺衍生的锂酰胺与简单的酮氧化剂原位氧化产生的。即使α位的碳氢键活性较低，具有现有α-取代基的胺也会发生区域选择性α'-氰化反应。胺α-芳基化可与α'-氰化反应相结合，在一次操作中生成双官能化产物。
相似文献
1
Regioselective α-Cyanation of Unprotected Alicyclic Amines.未保护脂环胺的区域选择性α-氰化反应
Org Lett. 2022 Sep 9;24(35):6364-6368. doi: 10.1021/acs.orglett.2c02148. Epub 2022 Aug 29.
2
Regioselective α-Phosphonylation of Unprotected Alicyclic Amines.未保护的脂环胺的区域选择性α-膦酰化反应
Org Lett. 2024 Jul 19;26(28):5972-5977. doi: 10.1021/acs.orglett.4c02037. Epub 2024 Jul 5.
3
Diversification of Unprotected Alicyclic Amines by C-H Bond Functionalization: Decarboxylative Alkylation of Transient Imines.未保护脂环族胺的 C-H 键功能化多样化：瞬态亚胺的脱羧烷基化反应。
Angew Chem Int Ed Engl. 2021 Jan 18;60(3):1625-1628. doi: 10.1002/anie.202011641. Epub 2020 Nov 17.
4
α-C-H Bond Functionalization of Unprotected Alicyclic Amines: Lewis-Acid-Promoted Addition of Enolates to Transient Imines.未保护脂环族胺的α-C-H键官能团化：路易斯酸促进烯醇盐加成到瞬态亚胺上
Org Lett. 2021 Feb 5;23(3):797-801. doi: 10.1021/acs.orglett.0c04024. Epub 2021 Jan 19.
5
Rapid functionalization of multiple C-H bonds in unprotected alicyclic amines.在未保护的脂环族胺中快速官能化多个 C-H 键。
Nat Chem. 2020 Jun;12(6):545-550. doi: 10.1038/s41557-020-0438-z. Epub 2020 Mar 30.
6
Synthesis of Polycyclic Imidazoles via α-C-H/N-H Annulation of Alicyclic Amines.通过脂环胺的α-C-H/N-H环化反应合成多环咪唑
Synthesis (Stuttg). 2023 Aug;55(15):2343-2352. doi: 10.1055/a-2022-1511. Epub 2023 Apr 13.
7
Synthesis of Polycyclic Isoindolines via α-C-H/N-H Annulation of Alicyclic Amines.通过脂环胺的α-C-H/N-H环化反应合成多环异吲哚啉
Org Lett. 2022 Feb 11;24(5):1224-1227. doi: 10.1021/acs.orglett.2c00018. Epub 2022 Jan 31.
8
α-C-H/N-H Annulation of Alicyclic Amines via Transient Imines: Preparation of Polycyclic Lactams.α-C-H/N-H 环化芳胺反应：通过瞬态亚胺制备多环内酰胺。
Org Lett. 2021 May 7;23(9):3729-3734. doi: 10.1021/acs.orglett.1c01125. Epub 2021 Apr 21.
9
Alicyclic-Amine-Derived Imine-BF Complexes: Easy-to-Make Building Blocks for the Synthesis of Valuable α-Functionalized Azacycles.脂环族胺衍生的亚胺 - 硼氟配合物：用于合成有价值的α-官能化氮杂环的易于制备的构建单元。
Angew Chem Int Ed Engl. 2024 Jan 2;63(1):e202313247. doi: 10.1002/anie.202313247. Epub 2023 Nov 27.
10
Continuous-flow oxidative cyanation of primary and secondary amines using singlet oxygen.使用单线态氧连续流氧化氰化伯胺和仲胺。
Angew Chem Int Ed Engl. 2014 Jan 7;53(2):557-61. doi: 10.1002/anie.201307778. Epub 2013 Nov 29.
引用本文的文献
1
Photocatalytic Decarboxylative Alkylation of Cyclic Imine-BF Complexes: A Modular Route to Functionalized Azacycles.环状亚胺 - BF 配合物的光催化脱羧烷基化反应：一种合成功能化氮杂环的模块化方法。
J Am Chem Soc. 2024 Sep 25;146(38):26331-26339. doi: 10.1021/jacs.4c08754. Epub 2024 Sep 12.
2
Regioselective α-Phosphonylation of Unprotected Alicyclic Amines.未保护的脂环胺的区域选择性α-膦酰化反应
Org Lett. 2024 Jul 19;26(28):5972-5977. doi: 10.1021/acs.orglett.4c02037. Epub 2024 Jul 5.
3
Transannular Functionalization of Multiple C(sp)-H Bonds of Tropane via an Alkene-Bridged Palladium(I) Dimer.通过烯烃桥连钯（I）二聚体实现托烷多个C（sp）-H键的跨环官能化
Organometallics. 2023 Apr 24;42(8):627-631. doi: 10.1021/acs.organomet.3c00086. Epub 2023 Apr 10.
4
Synthesis of Polycyclic Imidazoles via α-C-H/N-H Annulation of Alicyclic Amines.通过脂环胺的α-C-H/N-H环化反应合成多环咪唑
Synthesis (Stuttg). 2023 Aug;55(15):2343-2352. doi: 10.1055/a-2022-1511. Epub 2023 Apr 13.
5
Alicyclic-Amine-Derived Imine-BF Complexes: Easy-to-Make Building Blocks for the Synthesis of Valuable α-Functionalized Azacycles.脂环族胺衍生的亚胺 - 硼氟配合物：用于合成有价值的α-官能化氮杂环的易于制备的构建单元。
Angew Chem Int Ed Engl. 2024 Jan 2;63(1):e202313247. doi: 10.1002/anie.202313247. Epub 2023 Nov 27.
6
Palladium-Catalyzed Arylation of Endocyclic 1-Azaallyl Anions: Concise Synthesis of Unprotected Enantioenriched cis-2,3-Diarylpiperidines.钯催化的内环状1-氮杂烯丙基阴离子的芳基化反应：未保护的对映体富集的顺式-2,3-二芳基哌啶的简洁合成
Angew Chem Int Ed Engl. 2023 Sep 4;62(36):e202307638. doi: 10.1002/anie.202307638. Epub 2023 Jul 28.
本文引用的文献
1
-Functionalization of Saturated Aza-Heterocycles Enabled by Organic Photoredox Catalysis.- 有机光氧化还原催化实现的饱和氮杂环的功能化
ACS Catal. 2021 Mar 5;11(5):3153-3158. doi: 10.1021/acscatal.1c00099. Epub 2021 Feb 24.
2
Synthetic applications of hydride abstraction reactions by organic oxidants.有机氧化剂促进的氢化物转移反应的合成应用。
Chem Soc Rev. 2022 Jul 4;51(13):5660-5690. doi: 10.1039/d1cs01169c.
3
Modular Access to Chiral α-(Hetero)aryl Amines via Ni/Photoredox-Catalyzed Enantioselective Cross-Coupling.通过 Ni/光氧化还原催化的对映选择性交叉偶联实现手性 α-（杂）芳基胺的模块化方法。
J Am Chem Soc. 2022 May 18;144(19):8797-8806. doi: 10.1021/jacs.2c02795. Epub 2022 May 3.
4
Condensation-Based Methods for the C-H Bond Functionalization of Amines.基于缩合反应的胺类C-H键官能团化方法
Synthesis (Stuttg). 2021 Nov;53(21):3869-3908. doi: 10.1055/a-1631-2140. Epub 2021 Sep 2.
5
Photoinduced α-C-H Amination of Cyclic Amine Scaffolds Enabled by Polar-Radical Relay.光诱导的极性自由基接力促进环状胺骨架的α-C-H 胺化反应。
Angew Chem Int Ed Engl. 2022 Jun 20;61(25):e202202971. doi: 10.1002/anie.202202971. Epub 2022 Apr 25.
6
Nickel-Catalyzed Thermal Redox Functionalization of C(sp )-H Bonds with Carbon Electrophiles.镍催化碳（sp）-氢键与碳亲电试剂的热氧化还原官能化反应
Angew Chem Int Ed Engl. 2022 May 23;61(22):e202201662. doi: 10.1002/anie.202201662. Epub 2022 Mar 31.
7
Pd(II)-Catalyzed Enantioselective C(sp)-H Arylation of Cyclopropanes and Cyclobutanes Guided by Tertiary Alkylamines.钯(II)催化的三级烷基胺导向的环丙烷和环丁烷的对映选择性 C(sp3)-H 芳基化反应。
J Am Chem Soc. 2022 Mar 9;144(9):3939-3948. doi: 10.1021/jacs.1c11921. Epub 2022 Feb 25.
8
Synthesis of Polycyclic Isoindolines via α-C-H/N-H Annulation of Alicyclic Amines.通过脂环胺的α-C-H/N-H环化反应合成多环异吲哚啉
Org Lett. 2022 Feb 11;24(5):1224-1227. doi: 10.1021/acs.orglett.2c00018. Epub 2022 Jan 31.
9
Exploring Electrochemical C(sp)-H Oxidation for the Late-Stage Methylation of Complex Molecules.探索电化学 C(sp^3)-H 氧化在复杂分子晚期甲基化中的应用。
J Am Chem Soc. 2022 Jan 26;144(3):1187-1197. doi: 10.1021/jacs.1c09412. Epub 2022 Jan 11.
10
Electrochemical Desaturative β-Acylation of Cyclic N-Aryl Amines.电化学去饱和β-酰化环状 N-芳基胺。
Angew Chem Int Ed Engl. 2022 Feb 1;61(6):e202115178. doi: 10.1002/anie.202115178. Epub 2021 Dec 20.
Zotero 插件