• 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

金属介导的水相有机催化:[Ru(bpy)(nornicotine)]配合物催化Aldol 反应的偶然发现。

Metal-Mediated Organocatalysis in Water: Serendipitous Discovery of Aldol Reaction Catalyzed by the [Ru(bpy)(nornicotine)] Complex.

机构信息

CIQSO─Center for Research in Sustainable Chemistry and Department of Chemistry, University of Huelva, Campus de El Carmen s/n, Huelva E-21071, Spain.

出版信息

J Org Chem. 2022 Apr 15;87(8):5412-5418. doi: 10.1021/acs.joc.2c00472. Epub 2022 Mar 25.

DOI:10.1021/acs.joc.2c00472
PMID:35337184
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10550203/
Abstract

The [Ru(bpy)(Nor)] complex (Nor = nornicotine) is an efficient catalyst for the aldol reaction of acetone with activated benzaldehydes in a buffered aqueous solution. The metal plays the role of an activator for the nornicotine organocatalyst ligands. The resulting catalytic activity is potentiated by a factor of about 4.5 as compared to free nornicotine. Similar rate enhancements can be achieved by using Zn(II) cations as the activator. The observations are rationalized with the reduced basicity of the pyrrolidine N in nornicotine due to the enhanced electron withdrawal of the metal-complexed pyridyl moiety.

摘要

[Ru(bpy)(Nor)] 配合物(Nor = 降烟碱)是一种在缓冲水溶液中催化丙酮与活化苯甲醛的羟醛缩合反应的高效催化剂。金属在作为诺斯卡汀有机催化剂配体的激活剂方面发挥作用。与游离诺斯卡汀相比,所得催化活性增强约 4.5 倍。使用 Zn(II)阳离子作为激活剂也可以实现类似的速率增强。这些观察结果可以通过金属配合的吡啶部分增强电子抽出导致诺斯卡汀中吡咯烷 N 的碱性降低来合理化。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f371/10550203/70eda4cffb09/jo2c00472_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f371/10550203/622506fa1f64/jo2c00472_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f371/10550203/928a427000ff/jo2c00472_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f371/10550203/d2a695e77b16/jo2c00472_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f371/10550203/bad56a741ce3/jo2c00472_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f371/10550203/78effd20cc90/jo2c00472_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f371/10550203/bdbc0d3f4071/jo2c00472_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f371/10550203/70eda4cffb09/jo2c00472_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f371/10550203/622506fa1f64/jo2c00472_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f371/10550203/928a427000ff/jo2c00472_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f371/10550203/d2a695e77b16/jo2c00472_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f371/10550203/bad56a741ce3/jo2c00472_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f371/10550203/78effd20cc90/jo2c00472_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f371/10550203/bdbc0d3f4071/jo2c00472_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f371/10550203/70eda4cffb09/jo2c00472_0008.jpg

相似文献

1
Metal-Mediated Organocatalysis in Water: Serendipitous Discovery of Aldol Reaction Catalyzed by the [Ru(bpy)(nornicotine)] Complex.金属介导的水相有机催化:[Ru(bpy)(nornicotine)]配合物催化Aldol 反应的偶然发现。
J Org Chem. 2022 Apr 15;87(8):5412-5418. doi: 10.1021/acs.joc.2c00472. Epub 2022 Mar 25.
2
Nornicotine aqueous aldol reactions: synthetic and theoretical investigations into the origins of catalysis.降烟碱水相羟醛反应:催化起源的合成与理论研究
J Org Chem. 2004 Oct 1;69(20):6603-9. doi: 10.1021/jo048894j.
3
Aqueous aldol catalysis by a nicotine metabolite.尼古丁代谢物催化的水相羟醛反应
J Am Chem Soc. 2002 Apr 3;124(13):3220-1. doi: 10.1021/ja017774f.
4
Hammett correlation of nornicotine analogues in the aqueous aldol reaction: implications for green organocatalysis.降烟碱类似物在水相羟醛反应中的哈米特相关性:对绿色有机催化的启示。
J Org Chem. 2005 Apr 29;70(9):3705-8. doi: 10.1021/jo050161r.
5
Exploring the aldol reaction using catalytic antibodies and "on water" organocatalysts from QM/MM calculations.利用 QM/MM 计算研究使用催化抗体和“水相”有机催化剂的 aldol 反应。
J Am Chem Soc. 2014 Jan 8;136(1):147-56. doi: 10.1021/ja405614p. Epub 2013 Dec 17.
6
The nicotinic pharmacophore: thermodynamics of the hydrogen-bonding complexation of nicotine, nornicotine, and models.烟碱药效基团:尼古丁、去甲烟碱及其模型的氢键络合热力学
J Org Chem. 2003 Oct 17;68(21):8208-21. doi: 10.1021/jo035018h.
7
Nornicotine-organocatalyzed aqueous reduction of alpha,beta-unsaturated aldehydes.降烟碱-有机催化的α,β-不饱和醛的水相还原反应
Chem Commun (Camb). 2007 Dec 14(46):4952-4. doi: 10.1039/b713273e.
8
Investigating ionic effects applied to water based organocatalysed aldol reactions.研究应用于水相有机催化羟醛反应的离子效应。
Int J Mol Sci. 2011;12(12):9083-94. doi: 10.3390/ijms12129083. Epub 2011 Dec 7.
9
Site of protonation of nicotine and nornicotine in the gas phase: pyridine or pyrrolidine nitrogen?气相中尼古丁和去甲烟碱的质子化位点:吡啶氮还是吡咯烷氮?
J Am Chem Soc. 2002 Sep 4;124(35):10552-62. doi: 10.1021/ja017770a.
10
Asymmetric aldol reactions between acetone and benzaldehydes catalyzed by chiral Zn2+ complexes of aminoacyl 1,4,7,10-tetraazacyclododecane: fine-tuning of the amino-acid side chains and a revised reaction mechanism.手性 Zn2+ 配合物催化的丙酮与苯甲醛间的不对称羟醛反应:氨基酸侧链的精细调控和修订后的反应机理。
Chem Asian J. 2013 Sep;8(9):2125-35. doi: 10.1002/asia.201300308. Epub 2013 Jun 18.

本文引用的文献

1
Spotting trends in organocatalysis for the next decade.预测未来十年的有机催化趋势。
Nat Commun. 2020 Jul 29;11(1):3787. doi: 10.1038/s41467-020-17600-y.
2
Visible Light-Gated Organocatalysis Using a Ru -Photocage.可见光控有机催化反应中 Ru-光笼的应用
Chemistry. 2020 Nov 6;26(62):14229-14235. doi: 10.1002/chem.202001893. Epub 2020 Sep 30.
3
An efficient dynamic asymmetric catalytic system within a zinc-templated network.锌模板网络中的高效动态不对称催化体系。
Chem Commun (Camb). 2019 Jul 14;55(55):7970-7973. doi: 10.1039/c9cc03958a. Epub 2019 Jun 20.
4
Selective activation of organocatalysts by specific signals.通过特定信号对有机催化剂进行选择性激活。
Chem Sci. 2018 Jun 20;9(27):5999-6005. doi: 10.1039/c8sc02019a. eCollection 2018 Jul 21.
5
Water in asymmetric organocatalytic systems: a global perspective.不对称有机催化体系中的水:全球视角
Org Biomol Chem. 2016 Jul 14;14(26):6147-64. doi: 10.1039/c6ob00783j. Epub 2016 May 24.
6
Dynamic assembly of a zinc-templated bifunctional organocatalyst in the presence of water for the asymmetric aldol reaction.在水存在下用于不对称羟醛反应的锌模板双功能有机催化剂的动态组装
Chem Commun (Camb). 2015 Dec 21;51(98):17386-9. doi: 10.1039/c5cc07847d. Epub 2015 Oct 19.
7
Water-compatible hydrogen-bond activation: a scalable and organocatalytic model for the stereoselective multicomponent aza-Henry reaction.水兼容的氢键活化:一种用于立体选择性多组分氮杂-Henry反应的可扩展有机催化模型
Chemistry. 2013 Dec 2;19(49):16550-4. doi: 10.1002/chem.201303448. Epub 2013 Nov 4.
8
Catalytic asymmetric aldol reactions in aqueous media--a 5 year update.水相中的催化不对称Aldol 反应——5 年进展。
Chem Soc Rev. 2014 Jan 21;43(2):577-87. doi: 10.1039/c3cs60202h.
9
Direct asymmetric aldol reactions inspired by two types of natural aldolases: water-compatible organocatalysts and Zn(II) complexes.受两类天然醛缩酶启发的直接不对称醛醇反应:水相兼容的有机催化剂和 Zn(II)配合物。
J Org Chem. 2012 Jan 6;77(1):173-87. doi: 10.1021/jo201584w. Epub 2011 Dec 19.
10
Artificial light-gated catalyst systems.人工光控催化剂系统。
Angew Chem Int Ed Engl. 2010 Jul 12;49(30):5054-75. doi: 10.1002/anie.201000146.