手性芳基 1,2,4-三唑的催化不对称合成。
Catalytic Asymmetric Synthesis of Atropisomeric -Aryl 1,2,4-Triazoles.
机构信息
Department of Chemistry, Yale University, 225 Prospect Street, New Haven, Connecticut 06511-8107, United States.
出版信息
J Org Chem. 2023 Jun 16;88(12):7815-7820. doi: 10.1021/acs.joc.2c02727. Epub 2023 Jan 27.
Abstract
The atroposelective synthesis of -aryl 1,2,4-triazoles was developed. A cyclodehydration reaction was rendered asymmetric with the use of a chiral phosphoric acid catalyst to afford atropisomeric -aryl 1,2,4-triazoles in up to 91:9 er. Recrystallization of the isolated heterocycle further enriched the atropisomeric ratio of several analogs to 99:1 er or greater. A divergent and substrate-dependent reaction pathway yielding a different heterocyclic product is also disclosed.
摘要
手性膦酸催化的不对称环脱水反应实现了 -芳基 1,2,4-三唑的高对映选择性合成，产物的对映选择性高达 91:9。进一步对分离得到的杂环化合物进行重结晶，能够将几种类似物的对映体过量值提高至 99:1 或更高。此外，本文还揭示了一种具有发散性和底物依赖性的反应途径，可以得到不同的杂环产物。
相似文献
1
Catalytic Asymmetric Synthesis of Atropisomeric -Aryl 1,2,4-Triazoles.手性芳基 1,2,4-三唑的催化不对称合成。
J Org Chem. 2023 Jun 16;88(12):7815-7820. doi: 10.1021/acs.joc.2c02727. Epub 2023 Jan 27.
2
Organocatalytic Atroposelective Synthesis of Indole Derivatives Bearing Axial Chirality: Strategies and Applications.手性有机催化轴向手性吲哚衍生物的合成：策略与应用。
Acc Chem Res. 2022 Sep 20;55(18):2562-2580. doi: 10.1021/acs.accounts.2c00465. Epub 2022 Sep 2.
3
Divergent Control of Point and Axial Stereogenicity: Catalytic Enantioselective C-N Bond-Forming Cross-Coupling and Catalyst-Controlled Atroposelective Cyclodehydration.对映选择性和轴手性的控制策略：手性催化剂催化的 C-N 键形成交叉偶联反应和催化剂控制的轴手性环脱水反应。
Angew Chem Int Ed Engl. 2018 May 22;57(21):6251-6255. doi: 10.1002/anie.201802963. Epub 2018 Apr 23.
4
Construction of Non-Biaryl Atropisomeric Amide Scaffolds Bearing a C-N Axis via Enantioselective Catalysis.通过对映选择性催化构建具有 C-N 轴的非联苯非对映异构体酰胺骨架。
Molecules. 2022 Oct 4;27(19):6583. doi: 10.3390/molecules27196583.
5
Enantioselective Synthesis of Atropisomeric Anilides via Pd(II)-Catalyzed Asymmetric C-H Olefination.通过 Pd(II)催化的不对称 C-H 烯丙基化反应对映选择性合成非对映异构体苯胺。
J Am Chem Soc. 2020 Oct 21;142(42):18266-18276. doi: 10.1021/jacs.0c09400. Epub 2020 Oct 8.
6
Organocatalytic aryl-aryl bond formation: an atroposelective [3,3]-rearrangement approach to BINAM derivatives.有机催化的芳基-芳基键形成：BINAM 衍生物的非对映选择性 [3,3]-重排方法。
J Am Chem Soc. 2013 May 22;135(20):7414-7. doi: 10.1021/ja401709k. Epub 2013 May 9.
7
Atroposelective Synthesis of N-Arylated Quinoids by Organocatalytic Tandem N-Arylation/Oxidation.通过有机催化串联 N-芳基化/氧化反应对映选择性合成 N-芳基化的醌类化合物。
Angew Chem Int Ed Engl. 2022 Dec 5;61(49):e202212846. doi: 10.1002/anie.202212846. Epub 2022 Nov 9.
8
Catalytic Asymmetric Synthesis of Atropisomers Featuring an Aza Axis.基于氮杂轴的阻转异构体的催化不对称合成
Acc Chem Res. 2023 Sep 19;56(18):2537-2554. doi: 10.1021/acs.accounts.3c00419. Epub 2023 Sep 11.
9
Atroposelective Synthesis of 1,1'-Bipyrroles Bearing a Chiral N-N Axis: Chiral Phosphoric Acid Catalysis with Lewis Acid Induced Enantiodivergence.手性 N-N 轴联 1,1'-联吡啶的对映选择性合成：手性磷酸催化与路易斯酸诱导的对映体发散。
Angew Chem Int Ed Engl. 2022 Apr 11;61(16):e202200371. doi: 10.1002/anie.202200371. Epub 2022 Feb 24.
10
Carbene-catalyzed atroposelective synthesis of axially chiral styrenes.卡宾催化的轴手性苯乙烯的对映选择性合成。
Nat Commun. 2022 Jan 10;13(1):84. doi: 10.1038/s41467-021-27771-x.
引用本文的文献
1
All-round catalytic and atroposelective strategy via dynamic kinetic resolution for N-/2-/3-arylindoles.通过动态动力学拆分实现N-/2-/3-芳基吲哚的全方位催化和对映选择性策略。
Nat Commun. 2023 Sep 7;14(1):5502. doi: 10.1038/s41467-023-41299-2.
2
High-throughput determination of enantiopurity in atroposelective synthesis of aryl triazoles.芳基三唑的对映选择性合成中对映体纯度的高通量测定
Chem Sci. 2023 May 11;14(22):5992-5999. doi: 10.1039/d3sc01559a. eCollection 2023 Jun 7.
本文引用的文献
1
Asymmetric Synthesis of Axially Chiral C-N Atropisomers.轴手性 C-N 对映异构体的不对称合成。
Chemistry. 2022 May 16;28(28):e202104442. doi: 10.1002/chem.202104442. Epub 2022 Mar 25.
2
Organocatalytic Atroposelective Synthesis of N-N Axially Chiral Indoles and Pyrroles by De Novo Ring Formation.通过从头环化反应实现有机催化的N-N轴手性吲哚和吡咯的对映选择性合成。
Angew Chem Int Ed Engl. 2022 Apr 19;61(17):e202116829. doi: 10.1002/anie.202116829. Epub 2022 Feb 23.
3
Recent Advances in Catalytic Asymmetric Construction of Atropisomers.近年来手性轴手性化合物的催化不对称构建研究进展。
Chem Rev. 2021 Apr 28;121(8):4805-4902. doi: 10.1021/acs.chemrev.0c01306. Epub 2021 Mar 27.
4
Preclinical Lead Optimization of a 1,2,4-Triazole Based Tankyrase Inhibitor.基于 1,2,4-三唑的 Tankyrase 抑制剂的临床前先导优化。
J Med Chem. 2020 Jul 9;63(13):6834-6846. doi: 10.1021/acs.jmedchem.0c00208. Epub 2020 Jun 23.
5
Heterocycles in Medicinal Chemistry.杂环化合物在药物化学中的应用
Molecules. 2019 Oct 25;24(21):3839. doi: 10.3390/molecules24213839.
6
Organocatalytic Atroposelective Friedländer Quinoline Heteroannulation.有机催化非对映选择性 Friedländer 喹啉杂环化反应。
Org Lett. 2019 Jun 21;21(12):4831-4836. doi: 10.1021/acs.orglett.9b01731. Epub 2019 Jun 10.
7
Disparate Catalytic Scaffolds for Atroposelective Cyclodehydration.用于非对映选择性环脱水反应的不同催化支架。
J Am Chem Soc. 2019 Apr 24;141(16):6698-6705. doi: 10.1021/jacs.9b01911. Epub 2019 Apr 10.
8
Atropisomerism in medicinal chemistry: challenges and opportunities.手性药物化学中的对映异构现象：挑战与机遇。
Future Med Chem. 2018 Feb;10(4):409-422. doi: 10.4155/fmc-2017-0152. Epub 2018 Jan 30.
9
Brønsted acid-catalysed enantioselective construction of axially chiral arylquinazolinones.布朗斯特酸催化的手性轴芳香基喹唑啉酮的对映选择性构建。
Nat Commun. 2017 May 19;8:15489. doi: 10.1038/ncomms15489.
10
Discovery and Assessment of Atropisomers of (±)-Lesinurad.（±）-雷西纳德的阻转异构体的发现与评估
ACS Med Chem Lett. 2017 Feb 14;8(3):299-303. doi: 10.1021/acsmedchemlett.6b00465. eCollection 2017 Mar 9.
Zotero 插件