钯(II)/异喹啉催化剂促进的苄基磺酰胺的间-C-H 芳基化和烷基化反应。
meta-C-H Arylation and Alkylation of Benzylsulfonamide Enabled by a Palladium(II)/Isoquinoline Catalyst.
机构信息
Department of Chemistry, The Scripps Research Institute (TSRI), 10550 North Torrey Pines Road, La Jolla, CA, 92037, USA.
出版信息
Angew Chem Int Ed Engl. 2017 Jul 3;56(28):8183-8186. doi: 10.1002/anie.201704411. Epub 2017 Jun 9.
Abstract
Palladium(II)-catalyzed meta-C-H arylation and alkylation of benzylsulfonamide using 2-carbomethoxynorbornene (NBE-CO Me) as a transient mediator are realized by using a newly developed electron-deficient directing group and isoquinoline as a ligand. This protocol features broad substrate scope and excellent functional-group tolerance. The meta-substituted benyzlsulfonamides can be readily transformed into sodium sulfonates, sulfonate esters, and sulfonamides, as well as styrenes by Julia-type olefination. The unique impact of the isoquinoline ligand underscores the importance of subtle matching between ligands and the directing groups.
摘要
钯（II）催化的使用 2-羰甲氧降冰片烯（NBE-CO Me）作为瞬态介体的苄基磺酰胺的间 C-H 芳基化和烷基化反应，通过使用新开发的缺电子导向基团和异喹啉作为配体来实现。该方案具有广泛的底物范围和出色的官能团耐受性。间取代的苄基磺酰胺可以很容易地转化为磺酸钠、磺酸酯和磺酰胺，以及通过 Julia 型烯烃化转化为苯乙烯。异喹啉配体的独特影响强调了配体和导向基团之间微妙匹配的重要性。
相似文献
1
meta-C-H Arylation and Alkylation of Benzylsulfonamide Enabled by a Palladium(II)/Isoquinoline Catalyst.钯(II)/异喹啉催化剂促进的苄基磺酰胺的间-C-H 芳基化和烷基化反应。
Angew Chem Int Ed Engl. 2017 Jul 3;56(28):8183-8186. doi: 10.1002/anie.201704411. Epub 2017 Jun 9.
2
Ligand-Promoted meta-C-H Functionalization of Benzylamines.配体促进的苄胺的间 C-H 官能化。
Angew Chem Int Ed Engl. 2017 Apr 24;56(18):5125-5129. doi: 10.1002/anie.201701803. Epub 2017 Mar 30.
3
Functionalization of Sulfonamide-Containing Peptides through Late-Stage Palladium-Catalyzed C(sp)-H Arylation.通过晚期钯催化 C(sp)-H 芳基化反应对含磺酰胺肽进行功能化。
Org Lett. 2019 Aug 2;21(15):5858-5861. doi: 10.1021/acs.orglett.9b01953. Epub 2019 Jul 16.
4
Palladium(II)-catalyzed ortho-C-H arylation/alkylation of N-benzoyl α-amino ester derivatives.钯（II）催化的N-苯甲酰基α-氨基酯衍生物的邻位C-H芳基化/烷基化反应
Chemistry. 2014 Apr 14;20(16):4548-53. doi: 10.1002/chem.201304978. Epub 2014 Mar 13.
5
Palladium-catalyzed C(sp(3))-H Arylation of N-Boc benzylalkylamines via a deprotonative cross-coupling process.钯催化的N-叔丁氧羰基苄基烷基胺通过去质子化交叉偶联过程实现的C(sp(3))-H芳基化反应
Chemistry. 2015 Jul 27;21(31):11010-3. doi: 10.1002/chem.201502017. Epub 2015 Jun 30.
6
Pd-Catalyzed γ-C(sp)-H Arylation of Free Amines Using a Transient Directing Group.钯催化的利用瞬态导向基团的游离胺的γ-C(sp)-H 芳基化反应。
J Am Chem Soc. 2016 Nov 9;138(44):14554-14557. doi: 10.1021/jacs.6b09653. Epub 2016 Nov 1.
7
Catalytic intermolecular allylic C-H alkylation.催化分子间烯丙基C-H烷基化反应
J Am Chem Soc. 2008 Oct 29;130(43):14090-1. doi: 10.1021/ja806867p. Epub 2008 Oct 3.
8
Palladium(II)-Catalyzed Selective Arylation of Tertiary C-H Bonds of Cyclobutylmethyl Ketones Using Transient Directing Groups.钯(II)催化的使用瞬态导向基团的环丁基甲基酮的叔 C-H 键的选择性芳基化反应。
Angew Chem Int Ed Engl. 2022 Apr 25;61(18):e202117233. doi: 10.1002/anie.202117233. Epub 2022 Mar 9.
9
A useful Pd-catalyzed Negishi coupling approach to benzylic sulfonamide derivatives.一种用于制备苄基磺酰胺衍生物的有用的钯催化根岸偶联方法。
Org Lett. 2008 Jun 19;10(12):2517-20. doi: 10.1021/ol800785g. Epub 2008 May 21.
10
Palladium(II)-catalyzed C-H bond arylation of electron-deficient arenes at room temperature.钯（II）催化缺电子芳烃在室温下的C-H键芳基化反应。
Angew Chem Int Ed Engl. 2011 Feb 1;50(5):1076-9. doi: 10.1002/anie.201005990. Epub 2010 Dec 22.
引用本文的文献
1
A unified approach to -selective methylation, mono-, di- and trifluoromethylation of arenes.一种用于芳烃的 - 选择性甲基化、单氟甲基化、二氟甲基化和三氟甲基化的统一方法。
Chem Sci. 2025 Apr 10;16(19):8478-8486. doi: 10.1039/d5sc01367d. eCollection 2025 May 14.
2
Nitrogen atom insertion into indenes to access isoquinolines.通过在茚中插入氮原子来合成异喹啉。
Chem Sci. 2023 Feb 23;14(11):2954-2959. doi: 10.1039/d2sc06952k. eCollection 2023 Mar 15.
3
Sulfur-Phenolate Exchange as a Mild, Fast, and High-Yielding Method toward the Synthesis of Sulfonamides.硫酚交换作为一种温和、快速、高产率的合成磺酰胺的方法。
Org Lett. 2023 Feb 10;25(5):788-793. doi: 10.1021/acs.orglett.2c04292. Epub 2023 Jan 31.
4
Rhodium-catalyzed remote difunctionalization of arenes assisted by a relay directing group.通过接力导向基团辅助的铑催化芳烃远程双官能化反应
Chem Sci. 2022 May 30;13(24):7347-7354. doi: 10.1039/d2sc02205b. eCollection 2022 Jun 22.
5
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.
6
Regioselective C-H Functionalization of the Six-Membered Ring of the 6,5-Fused Heterocyclic Systems: An Overview.稠环 6,5-并杂环系统中环六员碳的区域选择性 C-H 官能化反应研究进展概述。
Molecules. 2021 Sep 23;26(19):5763. doi: 10.3390/molecules26195763.
7
Recyclable Ruthenium Catalyst for Distal meta-C-H Activation.可回收钌催化剂用于远程 meta-C-H 活化。
Chemistry. 2020 Nov 26;26(66):15290-15297. doi: 10.1002/chem.202003622. Epub 2020 Oct 22.
8
Palladium/Norbornene Cooperative Catalysis.钯/降冰片烯协同催化
Chem Rev. 2019 Jun 26;119(12):7478-7528. doi: 10.1021/acs.chemrev.9b00079. Epub 2019 Apr 25.
9
Palladium-Catalyzed Methylation of Aryl, Heteroaryl, and Vinyl Boronate Esters.钯催化的芳基、杂芳基和乙烯基硼酸酯的甲基化反应。
Org Lett. 2019 Mar 1;21(5):1337-1341. doi: 10.1021/acs.orglett.9b00025. Epub 2019 Feb 14.
10
A comprehensive overview of directing groups applied in metal-catalysed C-H functionalisation chemistry.指导基团在金属催化 C-H 官能化化学中的应用综述。
Chem Soc Rev. 2018 Aug 28;47(17):6603-6743. doi: 10.1039/c8cs00201k.
本文引用的文献
1
Computationally-Guided Development of a Chelated NHC-P Iridium(I) Complex for the Directed Hydrogen Isotope Exchange of Aryl Sulfones.用于芳基砜定向氢同位素交换的螯合NHC-P铱（I）配合物的计算指导开发
ACS Catal. 2020 Oct 2;10(19):11120-11126. doi: 10.1021/acscatal.0c03031. Epub 2020 Sep 1.
2
Directing group assisted -hydroxylation by C-H activation.导向基团辅助的C-H活化羟基化反应
Chem Sci. 2016 May 1;7(5):3147-3153. doi: 10.1039/c5sc04060d. Epub 2016 Jan 21.
3
Ligand-Promoted meta-C-H Functionalization of Benzylamines.配体促进的苄胺的间 C-H 官能化。
Angew Chem Int Ed Engl. 2017 Apr 24;56(18):5125-5129. doi: 10.1002/anie.201701803. Epub 2017 Mar 30.
4
Remote site-selective C-H activation directed by a catalytic bifunctional template.由催化双功能模板导向的远程位点选择性C-H活化
Nature. 2017 Mar 23;543(7646):538-542. doi: 10.1038/nature21418. Epub 2017 Mar 8.
5
Ligand Promoted meta-C-H Chlorination of Anilines and Phenols.配体促进的苯胺和酚的间 C-H 氯化反应。
J Am Chem Soc. 2016 Nov 16;138(45):14876-14879. doi: 10.1021/jacs.6b11055. Epub 2016 Nov 8.
6
Ligand-Promoted meta-C-H Amination and Alkynylation.配体促进的间位C-H胺化和炔基化反应。
J Am Chem Soc. 2016 Oct 26;138(42):14092-14099. doi: 10.1021/jacs.6b08942. Epub 2016 Oct 13.
7
Ion Pair-Directed Regiocontrol in Transition-Metal Catalysis: A Meta-Selective C-H Borylation of Aromatic Quaternary Ammonium Salts.离子对导向的过渡金属催化区域控制：芳基季铵盐的元选择性 C-H 硼化反应。
J Am Chem Soc. 2016 Oct 5;138(39):12759-12762. doi: 10.1021/jacs.6b08164. Epub 2016 Sep 21.
8
Ligand-Promoted Meta-C-H Arylation of Anilines, Phenols, and Heterocycles.配体促进的苯胺、酚和杂环的间-C-H 芳基化反应。
J Am Chem Soc. 2016 Jul 27;138(29):9269-76. doi: 10.1021/jacs.6b04966. Epub 2016 Jul 19.
9
Pd/Norbornene: A Winning Combination for Selective Aromatic Functionalization via C-H Bond Activation.钯/降冰片烯：通过 C-H 键活化实现选择性芳基功能化的理想组合。
Acc Chem Res. 2016 Jul 19;49(7):1389-400. doi: 10.1021/acs.accounts.6b00165. Epub 2016 Jun 22.
10
Meta-Selective CAr-H Nitration of Arenes through a Ru3(CO)12-Catalyzed Ortho-Metalation Strategy.通过 Ru3(CO)12 催化的邻位金属化策略实现芳烃的间选择性 CAr-H 硝化反应。
J Am Chem Soc. 2016 Jul 13;138(27):8470-5. doi: 10.1021/jacs.6b03402. Epub 2016 May 20.
Zotero 插件