• 文献检索
  • 文档翻译
  • 深度研究
  • 学术资讯
  • Suppr Zotero 插件Zotero 插件
  • 邀请有礼
  • 套餐&价格
  • 历史记录
应用&插件
Suppr Zotero 插件Zotero 插件浏览器插件Mac 客户端Windows 客户端微信小程序
定价
高级版会员购买积分包购买API积分包
服务
文献检索文档翻译深度研究API 文档MCP 服务
关于我们
关于 Suppr公司介绍联系我们用户协议隐私条款
关注我们

Suppr 超能文献

核心技术专利:CN118964589B侵权必究
粤ICP备2023148730 号-1Suppr @ 2026

文献检索

告别复杂PubMed语法,用中文像聊天一样搜索,搜遍4000万医学文献。AI智能推荐,让科研检索更轻松。

立即免费搜索

文件翻译

保留排版,准确专业,支持PDF/Word/PPT等文件格式,支持 12+语言互译。

免费翻译文档

深度研究

AI帮你快速写综述,25分钟生成高质量综述,智能提取关键信息,辅助科研写作。

立即免费体验

通过镓烷基跨金属捕获实现挑战性哒嗪的 LiTMP 锂化反应。

Transforming LiTMP Lithiation of Challenging Diazines through Gallium Alkyl Trans-Metal-Trapping.

机构信息

WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL, UK.

出版信息

Angew Chem Int Ed Engl. 2016 Oct 10;55(42):13147-13150. doi: 10.1002/anie.201607284.

DOI:10.1002/anie.201607284
PMID:27647741
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5113679/
Abstract

This study establishes a new trans-metal-trapping (TMT) procedure based on a mixture of LiTMP (the base) and tris(trimethylsilylmethyl)gallium [Ga(CH SiMe ) , GaR ] (the trap) that, operating in a tandem manner, is effective for the regioselective deprotonation of sensitive diazines in hydrocarbon solution, as illustrated through reactions of pyrazine, pyridazine, and pyrimidine, as well as through the N-S heterocycle benzothiazole. The metallo-activated complexes of all of these compounds were isolated and structurally defined.

摘要

本研究建立了一种基于 LiTMP(碱)和三(三甲基甲硅烷基)甲基镓[Ga(CH SiMe ) ,GaR](捕获剂)混合物的新型跨金属捕获(TMT)程序,该程序以串联方式操作,可有效实现烃溶液中敏感二嗪的区域选择性去质子化,如通过吡嗪、哒嗪和嘧啶以及 N-S 杂环苯并噻唑的反应所示。这些化合物的所有金属活化配合物均被分离并进行了结构定义。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/862e/5113679/d0e234096394/ANIE-55-13147-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/862e/5113679/5707e6077944/ANIE-55-13147-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/862e/5113679/1147420e9069/ANIE-55-13147-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/862e/5113679/f0b65b58ed61/ANIE-55-13147-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/862e/5113679/035948f94a19/ANIE-55-13147-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/862e/5113679/165f5b720632/ANIE-55-13147-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/862e/5113679/4992af241796/ANIE-55-13147-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/862e/5113679/d0e234096394/ANIE-55-13147-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/862e/5113679/5707e6077944/ANIE-55-13147-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/862e/5113679/1147420e9069/ANIE-55-13147-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/862e/5113679/f0b65b58ed61/ANIE-55-13147-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/862e/5113679/035948f94a19/ANIE-55-13147-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/862e/5113679/165f5b720632/ANIE-55-13147-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/862e/5113679/4992af241796/ANIE-55-13147-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/862e/5113679/d0e234096394/ANIE-55-13147-g008.jpg

相似文献

1
Transforming LiTMP Lithiation of Challenging Diazines through Gallium Alkyl Trans-Metal-Trapping.通过镓烷基跨金属捕获实现挑战性哒嗪的 LiTMP 锂化反应。
Angew Chem Int Ed Engl. 2016 Oct 10;55(42):13147-13150. doi: 10.1002/anie.201607284.
2
Trans-Metal-Trapping Meets Frustrated-Lewis-Pair Chemistry: Ga(CHSiMe)-Induced C-H Functionalizations.跨金属捕获与受阻路易斯酸碱对化学相遇:Ga(CHSiMe)引发的C-H官能团化反应
Inorg Chem. 2017 Aug 7;56(15):8615-8626. doi: 10.1021/acs.inorgchem.7b00549. Epub 2017 May 9.
3
LiTMP Trans-Metal-Trapping of Fluorinated Aromatic Molecules: A Comparative Study of Aluminum and Gallium Carbanion Traps.LiTMP 过渡金属捕获氟代芳烃分子:铝和镓碳负离子捕获剂的比较研究。
Angew Chem Int Ed Engl. 2017 Aug 1;56(32):9566-9570. doi: 10.1002/anie.201706064. Epub 2017 Jul 17.
4
Exploiting Coordination Effects for the Regioselective Zincation of Diazines Using TMPZnX⋅LiX (X=Cl, Br).利用TMPZnX⋅LiX(X = Cl,Br)实现二嗪区域选择性锌化的配位效应
Angew Chem Int Ed Engl. 2022 Oct 4;61(40):e202210491. doi: 10.1002/anie.202210491. Epub 2022 Sep 5.
5
Lithium-mediated zincation of pyrazine, pyridazine, pyrimidine, and quinoxaline.锂介导的吡嗪、哒嗪、嘧啶和喹喔啉的锌化反应。
J Org Chem. 2007 Aug 17;72(17):6602-5. doi: 10.1021/jo0708341. Epub 2007 Jul 27.
6
Trans-Metal-Trapping: Concealed Crossover Complexes En Route to Transmetallation?反金属捕获:通往转金属化的隐藏交叉配合物?
Chemistry. 2018 Jun 4;24(31):7786-7793. doi: 10.1002/chem.201800489. Epub 2018 Apr 30.
7
Adding a Structural Context to the Deprotometalation and Trans-Metal Trapping Chemistry of Phenyl-Substituted Benzotriazole.为苯基取代苯并三唑的去质子金属化和跨金属捕获化学添加结构背景。
Chemistry. 2015 Oct 12;21(42):14812-22. doi: 10.1002/chem.201502534. Epub 2015 Sep 21.
8
C-N Bond Activation and Ring Opening of a Saturated N-Heterocyclic Carbene by Lateral Alkali-Metal-Mediated Metalation.通过侧向碱金属介导的金属化作用实现 C-N 键活化和饱和 N-杂环卡宾的环开环反应。
Angew Chem Int Ed Engl. 2017 Jun 1;56(23):6632-6635. doi: 10.1002/anie.201702246. Epub 2017 May 10.
9
Complexes of an anionic gallium(I) N-heterocyclic carbene analogue with group 14 element(II) fragments: synthetic, structural and theoretical studies.阴离子型镓(I)氮杂环卡宾类似物与第14族元素(II)片段的配合物:合成、结构及理论研究
Inorg Chem. 2006 Sep 4;45(18):7242-51. doi: 10.1021/ic060851t.
10
Reactions of a gallium(II)-diazabutadiene dimer, [{{[(H)C(Bu(t))N]2}GaI}2], with [ME(SiMe3)2] (M = Li or Na; E = N, P, or As): structural, EPR, and ENDOR characterization of paramagnetic gallium(III) pnictide complexes.
Inorg Chem. 2005 Mar 21;44(6):2098-105. doi: 10.1021/ic0486825.

引用本文的文献

1
Arene Activation by Calcium Hydride/Zinc Amide Equilibration.通过氢化钙/锌酰胺平衡实现芳烃活化
J Am Chem Soc. 2025 Aug 13;147(32):29554-29567. doi: 10.1021/jacs.5c10735. Epub 2025 Aug 2.
2
Sodium mediated deprotonative borylation of arenes using sterically demanding B(CHSiMe): unlocking polybasic behaviour and competing lateral borane sodiation.使用空间位阻较大的B(CHSiMe)通过钠介导的芳烃去质子硼化反应:揭示多元行为和竞争性的硼氢化钠侧基反应
Chem Sci. 2023 May 5;14(24):6538-6545. doi: 10.1039/d3sc01705b. eCollection 2023 Jun 21.
3
Exploiting Coordination Effects for the Regioselective Zincation of Diazines Using TMPZnX⋅LiX (X=Cl, Br).

本文引用的文献

1
New in situ trapping metalations of functionalized arenes and heteroarenes with TMPLi in the presence of ZnCl2 and other metal salts.在 ZnCl2 和其他金属盐存在下,TMPLi 对功能化芳烃和杂芳烃的新型原位捕获金属化反应。
Angew Chem Int Ed Engl. 2014 Jul 21;53(30):7928-32. doi: 10.1002/anie.201403688. Epub 2014 Jun 12.
2
Regioselective metalations of pyrimidines and pyrazines by using frustrated Lewis pairs of BF3·OEt2 and hindered magnesium- and zinc-amide bases.利用BF3·OEt2受阻路易斯酸碱对以及受阻的镁酰胺和锌酰胺碱对嘧啶和吡嗪进行区域选择性金属化反应。
Angew Chem Int Ed Engl. 2013 Jun 24;52(26):6776-80. doi: 10.1002/anie.201301694. Epub 2013 May 23.
3
利用TMPZnX⋅LiX(X = Cl,Br)实现二嗪区域选择性锌化的配位效应
Angew Chem Int Ed Engl. 2022 Oct 4;61(40):e202210491. doi: 10.1002/anie.202210491. Epub 2022 Sep 5.
4
Enhancing Metalating Efficiency of the Sodium Amide NaTMP in Arene Borylation Applications.提高氨基钠NaTMP在芳烃硼化应用中的金属化效率。
Angew Chem Int Ed Engl. 2022 Jun 27;61(26):e202204262. doi: 10.1002/anie.202204262. Epub 2022 May 5.
5
Facilitating the Ferration of Aromatic Substrates through Intramolecular Sodium Mediation.通过分子内钠介导促进芳基底物的铁化。
Angew Chem Int Ed Engl. 2021 Jul 5;60(28):15296-15301. doi: 10.1002/anie.202104275. Epub 2021 Jun 17.
6
Synthetic and medicinal perspective of quinolines as antiviral agents.喹啉作为抗病毒药物的合成及药用前景。
Eur J Med Chem. 2021 Apr 5;215:113220. doi: 10.1016/j.ejmech.2021.113220. Epub 2021 Jan 24.
7
A Predictive Model Towards Site-Selective Metalations of Functionalized Heterocycles, Arenes, Olefins, and Alkanes using TMPZnCl⋅LiCl.一种使用TMPZnCl⋅LiCl对功能化杂环、芳烃、烯烃和烷烃进行位点选择性金属化的预测模型。
Angew Chem Int Ed Engl. 2020 Aug 24;59(35):14992-14999. doi: 10.1002/anie.202005372. Epub 2020 Jun 8.
8
Cobalt-Catalyzed Electrophilic Aminations with Anthranils: An Expedient Route to Condensed Quinolines.钴催化邻氨基苯甲酸的亲电胺化反应:合成稠合喹啉的便捷途径。
J Am Chem Soc. 2019 Jan 9;141(1):98-103. doi: 10.1021/jacs.8b11466. Epub 2018 Dec 21.
9
Donor-influenced Structure-Activity Correlations in Stoichiometric and Catalytic Reactions of Lithium Monoamido-Monohydrido-Dialkylaluminates.锂单酰胺-单氢化物-二烷基铝酸盐的计量和催化反应中供体影响的结构-活性关系。
Chemistry. 2018 Jul 11;24(39):9940-9948. doi: 10.1002/chem.201801541. Epub 2018 Jun 13.
10
LiTMP Trans-Metal-Trapping of Fluorinated Aromatic Molecules: A Comparative Study of Aluminum and Gallium Carbanion Traps.LiTMP 过渡金属捕获氟代芳烃分子:铝和镓碳负离子捕获剂的比较研究。
Angew Chem Int Ed Engl. 2017 Aug 1;56(32):9566-9570. doi: 10.1002/anie.201706064. Epub 2017 Jul 17.
New lithium-zincate approaches for the selective functionalisation of pyrazine: direct dideprotozincation vs. nucleophilic alkylation.
用于吡嗪选择性功能化的新型锂锌酸盐方法:直接双脱质子化与亲核烷基化。
Chem Commun (Camb). 2012 Feb 14;48(14):1985-7. doi: 10.1039/c2cc16959b. Epub 2012 Jan 11.
4
Deprotonative metalation of functionalized aromatics using mixed lithium-cadmium, lithium-indium, and lithium-zinc species.使用混合的锂-镉、锂-铟和锂-锌物种对功能化芳烃进行去质子化金属化。
Chemistry. 2009 Oct 5;15(39):10280-90. doi: 10.1002/chem.200901432.
5
TMPZnCl.LiCl: a new active selective base for the directed zincation of sensitive aromatics and heteroaromatics.TMPZnCl·LiCl:一种用于敏感芳烃和杂芳烃定向锌化的新型活性选择性碱
Org Lett. 2009 Apr 16;11(8):1837-40. doi: 10.1021/ol900342a.
6
Direct zincation of functionalized aromatics and heterocycles by using a magnesium base in the presence of ZnCl2.在氯化锌存在下,使用镁碱对官能化芳烃和杂环进行直接锌化反应。
Chemistry. 2009;15(2):457-68. doi: 10.1002/chem.200801558.
7
Deprotonative cadmation of functionalized aromatics.官能化芳烃的去质子化镉化反应
Chem Commun (Camb). 2008 Nov 14(42):5375-7. doi: 10.1039/b809543d. Epub 2008 Sep 17.
8
Functionalization of diazines and benzo derivatives through deprotonated intermediates.
Chem Soc Rev. 2008 Mar;37(3):595-609. doi: 10.1039/b709416g. Epub 2007 Nov 20.
9
Lithium-mediated zincation of pyrazine, pyridazine, pyrimidine, and quinoxaline.锂介导的吡嗪、哒嗪、嘧啶和喹喔啉的锌化反应。
J Org Chem. 2007 Aug 17;72(17):6602-5. doi: 10.1021/jo0708341. Epub 2007 Jul 27.
10
A new strategy for deprotonative functionalization of aromatics: transformations with excellent chemoselectivity and unique regioselectivities using t-Bu-P4 base.一种用于芳烃去质子官能化的新策略:使用叔丁基 - P4碱进行具有优异化学选择性和独特区域选择性的转化。
J Am Chem Soc. 2003 Jul 9;125(27):8082-3. doi: 10.1021/ja0342300.