• 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

铱催化的二烷基丙二酸酯的不对称烯丙基烷基化反应，实现了手性全碳季碳中心的构建。

Ir-Catalyzed Asymmetric Allylic Alkylation of Dialkyl Malonates Enabling the Construction of Enantioenriched All-Carbon Quaternary Centers.

机构信息

The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd., MC 101-20, Pasadena, California 91125, United States.

Alterome Therapeutics, 11440 West Bernardo Court Ste. 330, San Diego, California 92127, United States.

出版信息

J Am Chem Soc. 2022 May 11;144(18):7983-7987. doi: 10.1021/jacs.2c02960. Epub 2022 Apr 27.

DOI:10.1021/jacs.2c02960
PMID:35476460
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10038141/
Abstract

An enantioselective iridium-catalyzed allylic alkylation of malonates with trisubstituted allylic electrophiles to form all-carbon quaternary stereocenters is reported. This reaction proceeds at ambient temperature and enables the preparation of a wide range of enantioenriched products in up to 93% yield and 97% ee. The quaternary products can be readily converted to several valuable building blocks such as vicinal quaternary products and β-quaternary acids.

摘要

报道了一种对映选择性的铱催化丙二酸酯与三取代烯丙基亲电试剂的烯丙基烷基化反应，形成全碳季碳立体中心。该反应在环境温度下进行，能够以高达 93%的收率和 97%的对映体过量制备广泛的手性富集产物。季碳产物可以很容易地转化为几种有价值的构建块，如邻位季碳产物和β-季碳酸。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/731c/10038141/1bb74c476eaf/nihms-1874509-f0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/731c/10038141/9f40d4533ea2/nihms-1874509-f0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/731c/10038141/a7ece53d72b7/nihms-1874509-f0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/731c/10038141/7f9210677e81/nihms-1874509-f0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/731c/10038141/6f4519ebffa4/nihms-1874509-f0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/731c/10038141/1bb74c476eaf/nihms-1874509-f0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/731c/10038141/9f40d4533ea2/nihms-1874509-f0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/731c/10038141/a7ece53d72b7/nihms-1874509-f0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/731c/10038141/7f9210677e81/nihms-1874509-f0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/731c/10038141/6f4519ebffa4/nihms-1874509-f0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/731c/10038141/1bb74c476eaf/nihms-1874509-f0007.jpg

相似文献

1
Ir-Catalyzed Asymmetric Allylic Alkylation of Dialkyl Malonates Enabling the Construction of Enantioenriched All-Carbon Quaternary Centers.铱催化的二烷基丙二酸酯的不对称烯丙基烷基化反应，实现了手性全碳季碳中心的构建。
J Am Chem Soc. 2022 May 11;144(18):7983-7987. doi: 10.1021/jacs.2c02960. Epub 2022 Apr 27.
2
Enantioselective Synthesis of Vicinal All-Carbon Quaternary Centers via Iridium-Catalyzed Allylic Alkylation.通过铱催化的烯丙基烷基化反应实现非对映选择性合成毗邻全碳季碳中心。
Angew Chem Int Ed Engl. 2018 Jul 9;57(28):8664-8667. doi: 10.1002/anie.201804820. Epub 2018 Jun 11.
3
Construction of vicinal tertiary and all-carbon quaternary stereocenters via Ir-catalyzed regio-, diastereo-, and enantioselective allylic alkylation and applications in sequential Pd catalysis.通过 Ir 催化的区域、非对映和对映选择性烯丙基烷基化构建毗邻的三级和全碳季碳中心，并在顺序 Pd 催化中的应用。
J Am Chem Soc. 2013 Jul 24;135(29):10626-9. doi: 10.1021/ja4052075. Epub 2013 Jul 12.
4
Diastereo- and Enantioselective Construction of Vicinal All-Carbon Quaternary Stereocenters via Iridium/Europium Bimetallic Catalysis.通过铱/铕双金属催化，非对映选择性和对映选择性构建毗邻全碳季碳中心。
Angew Chem Int Ed Engl. 2022 Sep 26;61(39):e202208837. doi: 10.1002/anie.202208837. Epub 2022 Aug 18.
5
Iridium-Catalyzed Stereoselective Allylic Alkylation Reactions with Crotyl Chloride.铱催化的与氯代巴豆烯的立体选择性烯丙基烷基化反应。
Angew Chem Int Ed Engl. 2016 Dec 23;55(52):16092-16095. doi: 10.1002/anie.201609960. Epub 2016 Nov 28.
6
Enantioselective γ-Alkylation of α,β-Unsaturated Malonates and Ketoesters by a Sequential Ir-Catalyzed Asymmetric Allylic Alkylation/Cope Rearrangement.手性 Ir 催化的α,β-不饱和丙二酸酯和β-酮酯的连续不对称烯丙基烷基化/Cope 重排反应的对映选择性γ-烷基化。
J Am Chem Soc. 2016 Apr 27;138(16):5234-7. doi: 10.1021/jacs.6b02153. Epub 2016 Apr 18.
7
Enantio-, diastereo-, and regioselective iridium-catalyzed asymmetric allylic alkylation of acyclic β-ketoesters.非环β-酮酯的对映选择性、非对映选择性和区域选择性铱催化不对称烯丙基烷基化反应。
J Am Chem Soc. 2013 Nov 20;135(46):17298-301. doi: 10.1021/ja4097829. Epub 2013 Nov 6.
8
Synergistic Ir/Cu Catalysis for Asymmetric Allylic Alkylation of Oxindoles: Enantio- and Diastereoselective Construction of Quaternary and Tertiary Stereocenters.协同 Ir/Cu 催化的吲哚类化合物不对称烯丙基烷基化反应：对映选择性和非对映选择性构建季碳和叔碳中心。
Chemistry. 2021 Jul 16;27(40):10255-10260. doi: 10.1002/chem.202101267. Epub 2021 May 27.
9
Enantioselective Synthesis of Acyclic α-Quaternary Carboxylic Acid Derivatives through Iridium-Catalyzed Allylic Alkylation.通过铱催化的烯丙基烷基化反应实现非环 α-季碳羧酸衍生物的对映选择性合成。
Angew Chem Int Ed Engl. 2017 Sep 11;56(38):11545-11548. doi: 10.1002/anie.201707015. Epub 2017 Aug 9.
10
Intermolecular Stereoselective Iridium-Catalyzed Allylic Alkylation: An Evolutionary Account.分子间立体选择性铱催化烯丙基烷基化：一个发展历程
Synlett. 2018 Dec;29(19):2481-2492. doi: 10.1055/s-0037-1610217. Epub 2018 Aug 15.

引用本文的文献

1
Formation of Vicinal Secondary and All-Carbon Quaternary Stereocenters in Enantioenriched Diazenes via Branched-Selective Pd-Catalyzed Allylic Alkylation.通过支链选择性钯催化烯丙基烷基化反应在对映体富集的重氮化合物中形成邻位二级和全碳季碳立体中心。
Tetrahedron Lett. 2025 Jul 30;165-166. doi: 10.1016/j.tetlet.2025.155657. Epub 2025 May 16.
2
Experimental and Computational Studies on Cobalt(I)-Catalyzed Regioselective Allylic Alkylation Reactions.钴（I）催化的区域选择性烯丙基烷基化反应的实验与计算研究
Angew Chem Int Ed Engl. 2023 Nov 13;62(46):e202310129. doi: 10.1002/anie.202310129. Epub 2023 Oct 13.
3
Scope and Mechanistic Probe into Asymmetric Synthesis of α-Trisubstituted-α-Tertiary Amines by Rhodium Catalysis.

本文引用的文献

1
Construction of Vicinal Quaternary Centers via Iridium-Catalyzed Asymmetric Allenylic Alkylation of Racemic Tertiary Alcohols.通过铱催化的外消旋叔醇的不对称烯丙基烷基化反应构建偕季碳中心。
J Am Chem Soc. 2021 Mar 10;143(9):3323-3329. doi: 10.1021/jacs.1c00609. Epub 2021 Mar 1.
2
Recent Advances Regarding the Therapeutic Potential of Adapalene.关于阿达帕林治疗潜力的最新进展
Pharmaceuticals (Basel). 2020 Aug 28;13(9):217. doi: 10.3390/ph13090217.
3
Intermolecular Stereoselective Iridium-Catalyzed Allylic Alkylation: An Evolutionary Account.
铑催化α-三取代-α-叔胺不对称合成的范围及机理探究
J Am Chem Soc. 2023 Sep 13;145(36):19642-19654. doi: 10.1021/jacs.3c04211. Epub 2023 Aug 31.
4
Hydroxy-directed iridium-catalyzed enantioselective formal β-C(sp)-H allylic alkylation of α,β-unsaturated carbonyls.羟基导向的铱催化α,β-不饱和羰基化合物的对映选择性形式β-C(sp)-H烯丙基烷基化反应
Chem Sci. 2022 Oct 13;13(42):12491-12497. doi: 10.1039/d2sc03966d. eCollection 2022 Nov 2.
5
Borylated Cyclopropanes as Spring-Loaded Entities: Access to Vicinal Tertiary and Quaternary Carbon Stereocenters in Acyclic Systems.硼化环丙烷作为弹性能量载体：在非环体系中获得偕三级和四级碳立体中心。
J Am Chem Soc. 2022 Sep 14;144(36):16298-16302. doi: 10.1021/jacs.2c07394. Epub 2022 Aug 30.
分子间立体选择性铱催化烯丙基烷基化：一个发展历程
Synlett. 2018 Dec;29(19):2481-2492. doi: 10.1055/s-0037-1610217. Epub 2018 Aug 15.
4
Iridium-Catalyzed Asymmetric Synthesis of Functionally Rich Molecules Enabled by (Phosphoramidite,Olefin) Ligands.铱催化的通过（磷酰胺、烯烃）配体实现的功能丰富分子的不对称合成。
Acc Chem Res. 2019 Sep 17;52(9):2657-2672. doi: 10.1021/acs.accounts.9b00209. Epub 2019 Jun 19.
5
Enantioselective Ir-Catalyzed Allylic Alkylation of Racemic Allylic Alcohols with Malonates.对映选择性 Ir 催化的外消旋烯丙醇与丙二酸酯的烯丙基烷基化反应。
Org Lett. 2019 Feb 1;21(3):840-843. doi: 10.1021/acs.orglett.8b04143. Epub 2019 Jan 23.
6
Iridium-Catalyzed Asymmetric Allylic Substitution Reactions.铱催化的不对称烯丙基取代反应。
Chem Rev. 2019 Feb 13;119(3):1855-1969. doi: 10.1021/acs.chemrev.8b00506. Epub 2018 Dec 24.
7
Enantioselective Synthesis of Vicinal All-Carbon Quaternary Centers via Iridium-Catalyzed Allylic Alkylation.通过铱催化的烯丙基烷基化反应实现非对映选择性合成毗邻全碳季碳中心。
Angew Chem Int Ed Engl. 2018 Jul 9;57(28):8664-8667. doi: 10.1002/anie.201804820. Epub 2018 Jun 11.
8
Applications of Iridium-Catalyzed Asymmetric Allylic Substitution Reactions in Target-Oriented Synthesis.铱催化的不对称烯丙基取代反应在靶向合成中的应用。
Acc Chem Res. 2017 Oct 17;50(10):2539-2555. doi: 10.1021/acs.accounts.7b00300. Epub 2017 Sep 22.
9
Acyclic Quaternary Carbon Stereocenters via Enantioselective Transition Metal Catalysis.通过对映选择性过渡金属催化构建无环季碳立体中心
Chem Rev. 2017 Oct 11;117(19):12564-12580. doi: 10.1021/acs.chemrev.7b00385. Epub 2017 Sep 14.
10
Enantioselective Synthesis of Acyclic α-Quaternary Carboxylic Acid Derivatives through Iridium-Catalyzed Allylic Alkylation.通过铱催化的烯丙基烷基化反应实现非环 α-季碳羧酸衍生物的对映选择性合成。
Angew Chem Int Ed Engl. 2017 Sep 11;56(38):11545-11548. doi: 10.1002/anie.201707015. Epub 2017 Aug 9.