通过钯/降冰片烯协同催化实现远端烯基碳氢键官能团化
Distal Alkenyl C-H Functionalization via the Palladium/Norbornene Cooperative Catalysis.
作者信息
Wu Zhao, Fatuzzo Nina, Dong Guangbin
机构信息
Department of Chemistry , University of Chicago , Chicago , Illinois 60637 , United States.
出版信息
J Am Chem Soc. 2020 Feb 12;142(6):2715-2720. doi: 10.1021/jacs.9b11479. Epub 2020 Feb 3.
Abstract
A distal-selective alkenyl C-H arylation method is reported through a directed palladium/norbornene (Pd/NBE) cooperative catalysis. The key is to use an appropriate combination of the directing group and the NBE cocatalyst. A range of acyclic and cyclic -olefins are suitable substrates, and the reaction is operated under air with excellent site-selectivity. Preliminary mechanistic studies are consistent with the proposed Pd/NBE-catalyzed C-H activation instead of the Heck pathway. Initial success on distal alkylation has also been achieved using MeI and methyl bromoacetate as electrophiles.
摘要
通过定向钯/降冰片烯（Pd/NBE）协同催化，报道了一种远端选择性烯基C-H芳基化方法。关键在于使用导向基团和NBE助催化剂的适当组合。一系列无环和环状烯烃是合适的底物，该反应在空气中进行，具有出色的位点选择性。初步机理研究与所提出的Pd/NBE催化的C-H活化而非Heck途径一致。使用碘甲烷和溴乙酸甲酯作为亲电试剂，在远端烷基化方面也取得了初步成功。
相似文献
1
Distal Alkenyl C-H Functionalization via the Palladium/Norbornene Cooperative Catalysis.通过钯/降冰片烯协同催化实现远端烯基碳氢键官能团化
J Am Chem Soc. 2020 Feb 12;142(6):2715-2720. doi: 10.1021/jacs.9b11479. Epub 2020 Feb 3.
2
Palladium/norbornene-catalyzed distal alkenyl C-H arylation and alkylation of cis-olefins.钯/降冰片烯催化的顺式烯烃的远端烯基C-H芳基化和烷基化反应。
Tetrahedron. 2021 Jun 18;90. doi: 10.1016/j.tet.2021.132173. Epub 2021 May 11.
3
Modular ipso/ ortho Difunctionalization of Aryl Bromides via Palladium/Norbornene Cooperative Catalysis.通过钯/降冰片烯协同催化实现芳基溴化物的模块间 ipso/ortho 双官能化反应。
J Am Chem Soc. 2018 Jul 11;140(27):8551-8562. doi: 10.1021/jacs.8b04153. Epub 2018 Jun 27.
4
Structurally Modified Norbornenes: A Key Factor to Modulate Reaction Selectivity in the Palladium/Norbornene Cooperative Catalysis.结构修饰降冰片烯：调控钯/降冰片烯协同催化反应选择性的关键因素。
J Am Chem Soc. 2020 Oct 21;142(42):17859-17875. doi: 10.1021/jacs.0c09193. Epub 2020 Oct 5.
5
Mechanistic studies of Pd-catalyzed regioselective aryl C-H bond functionalization with strained alkenes: origin of regioselectivity.钯催化的稠环烯烃区域选择性芳基 C-H 键功能化反应的机理研究：区域选择性的起源。
Chemistry. 2011 Jul 11;17(29):8175-88. doi: 10.1002/chem.201100210. Epub 2011 Jun 3.
6
Direct Vicinal Difunctionalization of Thiophenes Enabled by the Palladium/Norbornene Cooperative Catalysis.钯/降冰片烯协同催化噻吩的直接邻位双官能化反应。
J Am Chem Soc. 2019 Dec 4;141(48):18958-18963. doi: 10.1021/jacs.9b10857. Epub 2019 Nov 22.
7
Selective C-2 alkylation of tryptophan by a Pd(II)/norbornene-promoted C-H activation reaction.钯（II）/降冰片烯促进的 C-H 活化反应实现色氨酸的选择性 C-2 烷基化。
J Org Chem. 2013 Dec 6;78(23):12263-7. doi: 10.1021/jo402107m. Epub 2013 Nov 15.
8
Modular and stereoselective synthesis of tetrasubstituted helical alkenes via a palladium-catalyzed domino reaction.通过钯催化的串联反应实现四取代螺旋烯烃的模块化和立体选择性合成。
Org Lett. 2012 Jul 20;14(14):3648-51. doi: 10.1021/ol301495q. Epub 2012 Jun 27.
9
Rapid and Modular Access to Multifunctionalized 1,2-Azaborines via Palladium/Norbornene Cooperative Catalysis.通过钯/降冰片烯协同催化快速模块化构建多功能化 1,2-氮杂硼烷。
J Am Chem Soc. 2024 Apr 10;146(14):9512-9518. doi: 10.1021/jacs.4c01582. Epub 2024 Mar 29.
10
Modular Entry to Functionalized Tetrahydrobenzo[]azepines via the Palladium/Norbornene Cooperative Catalysis Enabled by a C7-Modified Norbornene.通过 C7 修饰的降冰片烯实现钯/降冰片烯协同催化的模块化进入功能化四氢苯并[a]氮杂卓
J Am Chem Soc. 2021 Jul 7;143(26):9991-10004. doi: 10.1021/jacs.1c04575. Epub 2021 Jun 23.
引用本文的文献
1
Catalyst-controlled directing group translocation in the site selective C-H functionalization of 3-carboxamide indoles and metallocarbenes.催化剂控制的3-羧酰胺吲哚和金属卡宾的位点选择性C-H官能化中的导向基团迁移
Nat Commun. 2025 Jan 2;16(1):97. doi: 10.1038/s41467-024-55246-2.
2
Selective C-H Activation of Unprotected Allylamines by Control of Catalyst Speciation.通过控制催化剂形态实现未保护烯丙胺的选择性C-H活化
Chem Catal. 2023 Nov 16;3(11). doi: 10.1016/j.checat.2023.100809. Epub 2023 Nov 8.
3
Regio- and Stereoselective 1,2-Oxyhalogenation of Non-Conjugated Alkynes via Directed Nucleopalladation: Catalytic Access to Tetrasubstituted Alkenes.区域和立体选择性 1,2-卤化非共轭炔烃通过导向的钯络合反应：四取代烯烃的催化方法。
Angew Chem Int Ed Engl. 2022 Oct 24;61(43):e202209099. doi: 10.1002/anie.202209099. Epub 2022 Sep 29.
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
Pd -Catalyzed C(alkenyl)-H Activation Facilitated by a Transient Directing Group.钯催化的 C(烯基)-H 活化被瞬态导向基团促进。
Angew Chem Int Ed Engl. 2022 Jun 20;61(25):e202203624. doi: 10.1002/anie.202203624. Epub 2022 May 26.
6
Rapid Access to Multisubstituted Acrylamides from Cyclic Ketones via Palladium/Norbornene Cooperative Catalysis.通过钯/降冰片烯协同催化从环状酮快速获得多取代丙烯酰胺。
Angew Chem Int Ed Engl. 2022 Apr 19;61(17):e202201239. doi: 10.1002/anie.202201239. Epub 2022 Mar 4.
7
Palladium/Norbornene-Catalyzed Decarbonylative Difunctionalization of Thioesters.钯/降冰片烯催化硫酯的脱羰双官能化反应
JACS Au. 2021 Oct 15;1(11):1877-1884. doi: 10.1021/jacsau.1c00328. eCollection 2021 Nov 22.
8
Palladium-catalyzed C-H glycosylation and retro Diels-Alder tandem reaction structurally modified norbornadienes (smNBDs).钯催化的C-H糖基化与逆狄尔斯-阿尔德串联反应：结构修饰的降冰片二烯（smNBDs）
Chem Sci. 2021 Aug 31;12(39):13144-13150. doi: 10.1039/d1sc03569j. eCollection 2021 Oct 13.
9
Carbonyl 1,2-transposition through triflate-mediated α-amination.三氟甲磺酸酯介导的α-胺化的羰基 1,2-迁移。
Science. 2021 Nov 5;374(6568):734-740. doi: 10.1126/science.abl7854. Epub 2021 Nov 4.
10
Palladium/norbornene-catalyzed distal alkenyl C-H arylation and alkylation of cis-olefins.钯/降冰片烯催化的顺式烯烃的远端烯基C-H芳基化和烷基化反应。
Tetrahedron. 2021 Jun 18;90. doi: 10.1016/j.tet.2021.132173. Epub 2021 May 11.
本文引用的文献
1
Synthetic and Mechanistic Studies of a Versatile Heteroaryl Thioether Directing Group for Pd(II) Catalysis.用于钯（II）催化的多功能杂芳基硫醚导向基团的合成与机理研究
ACS Catal. 2019 Sep 6;9(9):7626-7640. doi: 10.1021/acscatal.9b01471. Epub 2019 Jul 2.
2
Modular and regioselective synthesis of all-carbon tetrasubstituted olefins enabled by an alkenyl Catellani reaction.通过烯基 Catellani 反应实现全碳四取代烯烃的模块化和区域选择性合成。
Nat Chem. 2019 Dec;11(12):1106-1112. doi: 10.1038/s41557-019-0358-y. Epub 2019 Nov 18.
3
Cobalt-Catalyzed Olefinic C-H Alkenylation/Alkylation Switched by Carbonyl Groups.羰基调控的钴催化烯烃C-H烯基化/烷基化反应
Org Lett. 2019 Oct 4;21(19):7772-7777. doi: 10.1021/acs.orglett.9b02717. Epub 2019 Sep 13.
4
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.
5
Palladium(II)-Initiated Catellani-Type Reactions.钯（II）引发的卡塔兰尼型反应。
Angew Chem Int Ed Engl. 2019 Apr 23;58(18):5832-5844. doi: 10.1002/anie.201813491. Epub 2019 Feb 20.
6
sp C-H activation -type directing groups.sp C-H活化型导向基团。
Chem Sci. 2018 Jan 17;9(6):1424-1432. doi: 10.1039/c7sc04768a. eCollection 2018 Feb 14.
7
The vinylogous Catellani reaction: a combined computational and experimental study.乙烯基类似物的卡泰拉尼反应：一项计算与实验相结合的研究。
Chem Sci. 2017 Nov 30;9(5):1191-1199. doi: 10.1039/c7sc04265e. eCollection 2018 Feb 7.
8
C(alkenyl)-H Activation via Six-Membered Palladacycles: Catalytic 1,3-Diene Synthesis.通过六元钯环实现 C(烯基)-H 活化：催化 1,3-二烯合成。
J Am Chem Soc. 2018 May 2;140(17):5805-5813. doi: 10.1021/jacs.8b02124. Epub 2018 Apr 23.
9
Synthesis of E- and Z-trisubstituted alkenes by catalytic cross-metathesis.通过催化交叉复分解合成 E-和 Z-三取代烯烃。
Nature. 2017 Dec 20;552(7685):347-354. doi: 10.1038/nature25002.
10
Chelation versus Non-Chelation Control in the Stereoselective Alkenyl sp C-H Bond Functionalization Reaction.手性螯合物与非螯合物控制的烯基 sp³ C-H 键的立体选择性官能化反应。
Angew Chem Int Ed Engl. 2017 Apr 24;56(18):5091-5095. doi: 10.1002/anie.201700559. Epub 2017 Mar 30.
Zotero 插件