配体促进的芳烃非定向 C-H 氰化反应。
Ligand-Promoted Non-Directed C-H Cyanation of Arenes.
机构信息
Department of Chemistry, The Scripps Research Institute (TSRI), 10550 North Torrey Pines Road, La Jolla, CA, 92037, USA.
Discovery Chemistry, Bristol-Myers Squibb Research and Development, 5 Research Parkway, Wallingford, CT, 06492, USA.
出版信息
Chemistry. 2019 Feb 11;25(9):2199-2202. doi: 10.1002/chem.201805772. Epub 2019 Jan 16.
Abstract
This article reports the first example of a 2-pyridone accelerated non-directed C-H cyanation with an arene as the limiting reagent. This protocol is compatible with a broad scope of arenes, including advanced intermediates, drug molecules, and natural products. A kinetic isotope experiment (k /k =4.40) indicates that the C-H bond cleavage is the rate-limiting step. Also, the reaction is readily scalable, further showcasing the synthetic utility of this method.
摘要
本文报道了首例以吡啶酮为加速剂、芳烃为限制试剂的非导向 C-H 氰化反应。该反应适用于多种芳烃底物，包括药物分子和天然产物等复杂结构的中间体。动力学同位素实验（k /k =4.40）表明 C-H 键断裂是决速步骤。此外，该反应可轻易放大规模，进一步展示了该方法的合成实用性。
相似文献
1
Ligand-Promoted Non-Directed C-H Cyanation of Arenes.配体促进的芳烃非定向 C-H 氰化反应。
Chemistry. 2019 Feb 11;25(9):2199-2202. doi: 10.1002/chem.201805772. Epub 2019 Jan 16.
2
Ligand-accelerated non-directed C-H functionalization of arenes.配体加速的芳烃非定向C-H官能团化反应
Nature. 2017 Nov 22;551(7681):489-493. doi: 10.1038/nature24632.
3
Ni-Catalyzed C-H Cyanation of (Hetero)arenes with 2-Cyanoisothiazolidine 1,1-Dioxide as a Cyanation Reagent.镍催化（杂）芳环与 2-氰基异噻唑啉 1,1-二氧化物的 C-H 氰化反应。
Org Lett. 2021 Apr 16;23(8):2868-2872. doi: 10.1021/acs.orglett.1c00468. Epub 2021 Mar 31.
4
Pd(II)-catalyzed aminotetrazole-directed ortho-selective halogenation of arenes.钯（II）催化的氨四唑导向的芳基邻位选择性卤化反应。
J Org Chem. 2013 Jun 21;78(12):6104-11. doi: 10.1021/jo400755q. Epub 2013 Jun 11.
5
Mechanism of the mild functionalization of arenes by diboron reagents catalyzed by iridium complexes. Intermediacy and chemistry of bipyridine-ligated iridium trisboryl complexes.铱配合物催化二硼试剂对芳烃的温和官能团化反应机理。联吡啶配位的三硼化铱配合物的中间体及化学性质。
J Am Chem Soc. 2005 Oct 19;127(41):14263-78. doi: 10.1021/ja053433g.
6
5-(Cyano)dibenzothiophenium Triflate: A Sulfur-Based Reagent for Electrophilic Cyanation and Cyanocyclizations.5-(氰基)二苯并噻吩𬭩三氟甲磺酸酯：一种用于亲电氰化和氰环化的基于硫的试剂。
Angew Chem Int Ed Engl. 2019 Jul 8;58(28):9496-9500. doi: 10.1002/anie.201904557. Epub 2019 Jun 6.
7
Remote meta-C-H Cyanation of Arenes Enabled by a Pyrimidine-Based Auxiliary.嘧啶基辅助剂实现芳基的远程 meta-C-H 氰化反应。
Angew Chem Int Ed Engl. 2017 Oct 2;56(41):12538-12542. doi: 10.1002/anie.201706360. Epub 2017 Sep 6.
8
Theoretical analysis of the mechanism of palladium(II) acetate-catalyzed oxidative Heck coupling of electron-deficient arenes with alkenes: effects of the pyridine-type ancillary ligand and origins of the meta-regioselectivity.钯（II）醋酸盐催化的缺电子芳环与烯烃的氧化 Heck 偶联反应的机理的理论分析：吡啶型辅助配体的影响和间位区域选择性的起源。
J Am Chem Soc. 2011 Dec 21;133(50):20218-29. doi: 10.1021/ja205294y. Epub 2011 Nov 23.
9
Acetonitrile as a cyanating reagent: Cu-catalyzed cyanation of arenes.乙腈作为一种氰化试剂：铜催化的芳烃氰化反应
Org Lett. 2015 Jun 5;17(11):2602-5. doi: 10.1021/acs.orglett.5b00886. Epub 2015 May 19.
10
Electrochemical C-H Cyanation of Electron-Rich (Hetero)Arenes.电化学富电子（杂）芳环的 C-H 氰化反应。
Chemistry. 2018 Aug 6;24(44):11288-11291. doi: 10.1002/chem.201802247. Epub 2018 Jul 10.
引用本文的文献
1
Ligand-Controlled Nondirected - or -C-H Olefination of Silyl-Protected Phenols.配体控制的硅基保护酚的非定向或C-H烯烃化反应
ACS Catal. 2024 Sep 6;14(17):12806-12813. doi: 10.1021/acscatal.4c03858. Epub 2024 Aug 9.
2
Palladium-Catalyzed Non-Directed C─H Functionalization of Arenes with Trifluoromethylated Olefins.钯催化芳烃与三氟甲基化烯烃的非定向C─H官能团化反应
Chemistry. 2025 Aug 21;31(47):e01973. doi: 10.1002/chem.202501973. Epub 2025 Jul 23.
3
Remote C-H Olefination of Heterocyclic Biaryls Enabled by Reversibly Bound Templates.可逆结合模板实现杂环联芳基的远程C-H烯基化反应
Angew Chem Int Ed Engl. 2023 Sep 11;62(37):e202307581. doi: 10.1002/anie.202307581. Epub 2023 Aug 7.
4
Dual-Ligand Catalyst for the Nondirected C-H Olefination of Heteroarenes.双配体催化剂用于杂芳烃的非导向 C-H 烯烃化反应。
J Am Chem Soc. 2023 Apr 12;145(14):8198-8208. doi: 10.1021/jacs.3c01631. Epub 2023 Mar 28.
5
Mechanistic studies of the palladium-catalyzed S,O-ligand promoted C-H olefination of aromatic compounds.钯催化的S，O-配体促进芳香族化合物C-H烯基化反应的机理研究
Chem Sci. 2023 Feb 16;14(11):2943-2953. doi: 10.1039/d2sc06840k. eCollection 2023 Mar 15.
6
Dual ligand approach increases functional group tolerance in the Pd-catalysed C-H arylation of -heterocyclic pharmaceuticals.双配体方法提高了钯催化的杂环药物C-H芳基化反应中的官能团耐受性。
Chem Sci. 2023 Jan 10;14(5):1176-1183. doi: 10.1039/d2sc04911b. eCollection 2023 Feb 1.
7
Facile synthesis of 6-organyl-4-(trifluoromethyl)pyridin-2(1)-ones and their polyfluoroalkyl-containing analogs.6-有机基-4-(三氟甲基)吡啶-2(1)-酮及其含多氟烷基类似物的简便合成
Russ Chem Bull. 2022;71(8):1687-1700. doi: 10.1007/s11172-022-3579-y. Epub 2022 Sep 23.
8
Silver-Free C-H Activation: Strategic Approaches towards Realizing the Full Potential of C-H Activation in Sustainable Organic Synthesis.无银碳氢活化：实现碳氢活化在可持续有机合成中全部潜力的策略方法。
Angew Chem Int Ed Engl. 2022 Nov 25;61(48):e202210825. doi: 10.1002/anie.202210825. Epub 2022 Oct 21.
9
Site-Selective C-H Arylation of Diverse Arenes Ortho to Small Alkyl Groups.对位小烷基取代芳烃的位点选择性 C-H 芳基化反应。
Angew Chem Int Ed Engl. 2022 Sep 26;61(39):e202205470. doi: 10.1002/anie.202205470. Epub 2022 Aug 23.
10
S,O-Ligand Promoted meta-C-H Arylation of Anisole Derivatives via Palladium/Norbornene Catalysis.S，O-配体通过钯/降冰片烯催化促进苯甲醚衍生物的间位C-H芳基化反应。
Angew Chem Int Ed Engl. 2022 Aug 1;61(31):e202201750. doi: 10.1002/anie.202201750. Epub 2022 Jun 21.
本文引用的文献
1
Ligand-Enabled γ-C(sp)-H Activation of Ketones.配体促进的酮的 γ-C(sp 3 )-H 活化
J Am Chem Soc. 2018 Mar 14;140(10):3564-3568. doi: 10.1021/jacs.8b01359. Epub 2018 Mar 2.
2
Ligand-accelerated non-directed C-H functionalization of arenes.配体加速的芳烃非定向C-H官能团化反应
Nature. 2017 Nov 22;551(7681):489-493. doi: 10.1038/nature24632.
3
Remote meta-C-H Cyanation of Arenes Enabled by a Pyrimidine-Based Auxiliary.嘧啶基辅助剂实现芳基的远程 meta-C-H 氰化反应。
Angew Chem Int Ed Engl. 2017 Oct 2;56(41):12538-12542. doi: 10.1002/anie.201706360. Epub 2017 Sep 6.
4
Direct C-H Cyanation of Arenes via Organic Photoredox Catalysis.芳烃的有机光氧化还原催化直接 C-H 氰化反应。
J Am Chem Soc. 2017 Mar 1;139(8):2880-2883. doi: 10.1021/jacs.6b12708. Epub 2017 Feb 14.
5
Ruthenium-Catalyzed Direct and Selective C-H Cyanation of N-(Hetero)aryl-7-azaindoles.钌催化的 N-(杂芳基)-7-氮杂吲哚的直接选择性 C-H 氰化反应。
J Org Chem. 2016 Aug 5;81(15):6525-34. doi: 10.1021/acs.joc.6b01148. Epub 2016 Jul 22.
6
Ligand-Enabled Arylation of γ-C-H Bonds.配体促进的γ-C-H键芳基化反应
Angew Chem Int Ed Engl. 2016 Mar 18;55(13):4317-21. doi: 10.1002/anie.201512020. Epub 2016 Feb 25.
7
Rhodium-Catalyzed Cyanation of C(sp(2))-H Bond of Alkenes.铑催化的烯烃 C(sp(2))-H 键氰化反应。
Org Lett. 2015 Aug 7;17(15):3766-9. doi: 10.1021/acs.orglett.5b01746. Epub 2015 Jul 21.
8
Co(III)-catalyzed C-H activation/formal SN-type reactions: selective and efficient cyanation, halogenation, and allylation.钴(III)催化的 C-H 活化/形式 SN 型反应：选择性和高效的氰化、卤化和烯丙基化反应。
J Am Chem Soc. 2014 Dec 24;136(51):17722-5. doi: 10.1021/ja511011m. Epub 2014 Dec 10.
9
Iron(II)-catalyzed direct cyanation of arenes with aryl(cyano)iodonium triflates.铁(II)催化芳基(氰基)碘𬭩三氟甲磺酸酯对芳烃的直接氰化反应。
Angew Chem Int Ed Engl. 2014 Feb 17;53(8):2186-9. doi: 10.1002/anie.201309791. Epub 2014 Jan 22.
10
Rhodium-catalyzed directed C-H cyanation of arenes with N-cyano-N-phenyl-p-toluenesulfonamide.铑催化的 N-氰基-N-苯基对甲苯磺酰胺导向的芳基 C-H 氰化反应。
J Am Chem Soc. 2013 Jul 24;135(29):10630-3. doi: 10.1021/ja405742y. Epub 2013 Jul 12.
Zotero 插件