• 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

通过钴（II）基金属自由基催化实现α-重氮乙酸酯的立体选择性分子内环丙烷化反应。

Stereoselective Intramolecular Cyclopropanation of α-Diazoacetates via Co(II)-Based Metalloradical Catalysis.

作者信息

Ruppel Joshua V, Cui Xin, Xu Xue, Zhang X Peter

出版信息

Org Chem Front. 2014 Jul 1;1(5):515-520. doi: 10.1039/C4QO00041B.

DOI:10.1039/C4QO00041B
PMID:24910778
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC4043383/
Abstract

Co(II) complexes of -symmetric chiral porphyrins have been proven to be effective metalloradical catalysts for the asymmetric intramolecular cyclopropanation of allyl α-diazoacetates. 4-(Dimethylamino)pyridine (DMAP), through positive effect, plays an important role in the enhancement of the asymmetric induction for the intramolecular cyclopropanation process. This metalloradical catalytic system is suitable for cyclopropanation of allyl α-diazoacetates with varied functional groups and substitution patterns, producing bicyclic products with complete diastereocontrol and good enantiocontrol.

摘要

对称手性卟啉的钴（II）配合物已被证明是用于烯丙基α-重氮乙酸酯不对称分子内环丙烷化反应的有效金属自由基催化剂。4-（二甲基氨基）吡啶（DMAP）通过正效应，在增强分子内环丙烷化反应的不对称诱导中发挥重要作用。这种金属自由基催化体系适用于具有不同官能团和取代模式的烯丙基α-重氮乙酸酯的环丙烷化反应，可生成具有完全非对映体控制和良好对映体控制的双环产物。

相似文献

1
Stereoselective Intramolecular Cyclopropanation of α-Diazoacetates via Co(II)-Based Metalloradical Catalysis.通过钴（II）基金属自由基催化实现α-重氮乙酸酯的立体选择性分子内环丙烷化反应。
Org Chem Front. 2014 Jul 1;1(5):515-520. doi: 10.1039/C4QO00041B.
2
Highly asymmetric intramolecular cyclopropanation of acceptor-substituted diazoacetates by Co(II)-based metalloradical catalysis: iterative approach for development of new-generation catalysts.受主取代重氮乙酸酯的钴(II)基金属自由基催化的高非对映选择性分子内环丙烷化：新一代催化剂的发展的迭代方法。
J Am Chem Soc. 2011 Oct 5;133(39):15292-5. doi: 10.1021/ja2062506. Epub 2011 Sep 8.
3
Enantioselective Cyclopropanation of a Wide Variety of Olefins Catalyzed by Ru(II)-Pheox Complexes.手性钌（II）-菲咯啉配合物催化的各种烯烃的对映选择性环丙烷化反应。
Acc Chem Res. 2016 Oct 18;49(10):2080-2090. doi: 10.1021/acs.accounts.6b00070. Epub 2016 Sep 20.
4
Metalloradical Activation of In Situ-Generated α-Alkynyldiazomethanes for Asymmetric Radical Cyclopropanation of Alkenes.原位生成的α-炔基重氮甲烷的金属自由基活化用于烯烃的不对称自由基环丙烷化反应。
J Am Chem Soc. 2022 Feb 9;144(5):2368-2378. doi: 10.1021/jacs.1c13154. Epub 2022 Jan 31.
5
Asymmetric Radical Cyclopropanation of Dehydroaminocarboxylates: Stereoselective Synthesis of Cyclopropyl α-Amino Acids.脱氢氨基羧酸盐的不对称自由基环丙烷化反应：环丙基α-氨基酸的立体选择性合成
Chem. 2021 Jun 10;7(6):1588-1601. doi: 10.1016/j.chempr.2021.03.002. Epub 2021 Mar 29.
6
Comparative enantiocontrol with allyl phenyldiazoacetates in asymmetric catalytic intramolecular cyclopropanation.在不对称催化分子内环丙烷化反应中，烯丙基苯基重氮乙酸酯的对映体控制比较
Chirality. 2003 May 5;15(4):369-73. doi: 10.1002/chir.10219.
7
Asymmetric inter- and intramolecular cyclopropanation of alkenes catalyzed by chiral ruthenium porphyrins. Synthesis and crystal structure of a chiral metalloporphyrin carbene complex.手性钌卟啉催化烯烃的不对称分子间和分子内环丙烷化反应。一种手性金属卟啉卡宾配合物的合成与晶体结构。
J Am Chem Soc. 2001 May 9;123(18):4119-29. doi: 10.1021/ja001416f.
8
Asymmetric Radical Cyclopropanation of Alkenes with In Situ-Generated Donor-Substituted Diazo Reagents via Co(II)-Based Metalloradical Catalysis.通过基于 Co(II)的金属自由基催化，通过原位生成供体取代重氮试剂实现烯烃的不对称自由基环丙烷化反应。
J Am Chem Soc. 2017 Jan 25;139(3):1049-1052. doi: 10.1021/jacs.6b11336. Epub 2017 Jan 12.
9
Metalloradical activation of α-formyldiazoacetates for the catalytic asymmetric radical cyclopropanation of alkenes.金属自由基活化α-甲酰基重氮乙酸酯用于烯烃的催化不对称自由基环丙烷化反应
Chem Sci. 2017 Jun 1;8(6):4347-4351. doi: 10.1039/c7sc00658f. Epub 2017 Mar 31.
10
Next-Generation D -Symmetric Chiral Porphyrins for Cobalt(II)-Based Metalloradical Catalysis: Catalyst Engineering by Distal Bridging.用于钴（II）基金属自由基催化的下一代D-对称手性卟啉：通过远端桥连进行催化剂工程设计
Angew Chem Int Ed Engl. 2019 Feb 25;58(9):2670-2674. doi: 10.1002/anie.201812379. Epub 2019 Feb 4.

引用本文的文献

1
Light Induced Cobalt(III) Carbene Radical Formation from Dimethyl Malonate As Carbene Precursor.以丙二酸二甲酯为卡宾前体光诱导形成钴（III）卡宾自由基
Organometallics. 2024 May 24;43(11):1299-1307. doi: 10.1021/acs.organomet.4c00127. eCollection 2024 Jun 10.
2
Metalloradical Catalysis: General Approach for Controlling Reactivity and Selectivity of Homolytic Radical Reactions.金属自由基催化：控制均裂自由基反应的反应性和选择性的通用方法。
Angew Chem Int Ed Engl. 2024 May 13;63(20):e202320243. doi: 10.1002/anie.202320243. Epub 2024 Apr 3.
3
Cu(ii)-mediated direct intramolecular cyclopropanation of distal olefinic acetate: access to cyclopropane-fused γ-lactones.铜（II）介导的远端醋酸烯丙酯的直接分子内环丙烷化反应：合成环丙烷稠合的γ-内酯
Chem Sci. 2023 May 25;14(24):6663-6668. doi: 10.1039/d3sc01752d. eCollection 2023 Jun 21.
4
Carbene Radicals in Transition-Metal-Catalyzed Reactions.过渡金属催化反应中的卡宾自由基
ACS Catal. 2023 Apr 6;13(8):5428-5448. doi: 10.1021/acscatal.3c00591. eCollection 2023 Apr 21.
5
Transition Metal Catalysis Controlled by Hydrogen Bonding in the Second Coordination Sphere.氢键在第二配位球中控制的过渡金属催化作用。
Chem Rev. 2022 Jul 27;122(14):12308-12369. doi: 10.1021/acs.chemrev.1c00862. Epub 2022 May 20.
6
Cobalt(II)-tetraphenylporphyrin-catalysed carbene transfer from acceptor-acceptor iodonium ylides via N-enolate-carbene radicals.钴(II)四苯基卟啉催化的受主-受主碘𬭩叶立德经由 N-烯醇化物-卡宾自由基的碳烯转移。
Nat Chem. 2022 May;14(5):550-557. doi: 10.1038/s41557-022-00905-4. Epub 2022 Mar 24.
7
Revisiting the Electronic Structure of Cobalt Porphyrin Nitrene and Carbene Radicals with NEVPT2-CASSCF Calculations: Doublet versus Quartet Ground States.用NEVPT2-CASSCF计算重新审视钴卟啉氮烯和卡宾自由基的电子结构：二重态与四重态基态
Inorg Chem. 2021 Jun 21;60(12):8380-8387. doi: 10.1021/acs.inorgchem.1c00910. Epub 2021 Jun 5.
8
Co-Catalyzed Transannulation of Pyridotriazoles with Isothiocyanates and Xanthate Esters.偕二氮杂茂与异硫氰酸酯和黄原酸酯的共催化转环反应。
Org Lett. 2020 Nov 6;22(21):8500-8504. doi: 10.1021/acs.orglett.0c03099. Epub 2020 Oct 12.
9
Carbene Transfer Reactions Catalysed by Dyes of the Metalloporphyrin Group.金属卟啉类染料催化的卡宾转移反应。
Molecules. 2018 Mar 29;23(4):792. doi: 10.3390/molecules23040792.

本文引用的文献

1
Cobalt(II)-catalyzed asymmetric olefin cyclopropanation with α-ketodiazoacetates.钴（II）催化的α-重氮乙酰乙酸酯参与的不对称烯烃环丙烷化反应
Angew Chem Int Ed Engl. 2013 Nov 4;52(45):11857-61. doi: 10.1002/anie.201305883. Epub 2013 Sep 20.
2
Highly asymmetric intramolecular cyclopropanation of acceptor-substituted diazoacetates by Co(II)-based metalloradical catalysis: iterative approach for development of new-generation catalysts.受主取代重氮乙酸酯的钴(II)基金属自由基催化的高非对映选择性分子内环丙烷化：新一代催化剂的发展的迭代方法。
J Am Chem Soc. 2011 Oct 5;133(39):15292-5. doi: 10.1021/ja2062506. Epub 2011 Sep 8.
3
Asymmetric inter- and intramolecular cyclopropanation reactions catalyzed by a reusable macroporous-polymer-supported chiral ruthenium(II)/phenyloxazoline complex.一种可重复使用的大孔聚合物负载手性钌（II）/苯基恶唑啉配合物催化的不对称分子间和分子内环丙烷化反应。
Angew Chem Int Ed Engl. 2010 Nov 2;49(45):8439-43. doi: 10.1002/anie.201002240.
4
A general and efficient cobalt(II)-based catalytic system for highly stereoselective cyclopropanation of alkenes with α-cyanodiazoacetates.一种通用且高效的钴（II）基催化体系，用于高度立体选择性地催化烯烃与α-氰基重氮乙酸酯的环丙烷化反应。
J Am Chem Soc. 2010 Sep 22;132(37):12796-9. doi: 10.1021/ja1056246.
5
'Carbene radicals' in Co(II)(por)-catalyzed olefin cyclopropanation.钴(II)(卟啉)催化烯烃环丙烷化反应中的卡宾自由基。
J Am Chem Soc. 2010 Aug 11;132(31):10891-902. doi: 10.1021/ja103768r.
6
Chiral bis(oxazolinyl)phenyl Ru(II) catalysts for highly enantioselective cyclopropanation.用于高对映选择性环丙烷化反应的手性双（恶唑啉基）苯基钌（II）催化剂
Chemistry. 2010 May 3;16(17):4986-90. doi: 10.1002/chem.200903514.
7
Heterocycles from cyclopropanes: applications in natural product synthesis.环丙烷衍生的杂环化合物：在天然产物合成中的应用。
Chem Soc Rev. 2009 Nov;38(11):3051-60. doi: 10.1039/b901245c. Epub 2009 Jul 10.
8
cis-Beta-bis(carbonyl) ruthenium-salen complexes: X-ray crystal structures and remarkable catalytic properties toward asymmetric intramolecular alkene cyclopropanation.顺式-β-双（羰基）钌-萨伦配合物：X射线晶体结构及对分子内不对称烯烃环丙烷化的显著催化性能
J Am Chem Soc. 2009 Apr 1;131(12):4405-17. doi: 10.1021/ja8086399.
9
Acceptor/acceptor-substituted diazo reagents for carbene transfers: cobalt-catalyzed asymmetric Z-cyclopropanation of alkenes with alpha-nitrodiazoacetates.用于卡宾转移的受体/受体取代重氮试剂：钴催化的α-硝基重氮乙酸酯与烯烃的不对称Z-环丙烷化反应
Angew Chem Int Ed Engl. 2008;47(44):8460-3. doi: 10.1002/anie.200803857.
10
Chiral bis(pyridylimino)isoindoles: a highly modular class of pincer ligands for enantioselective catalysis.手性双（吡啶基亚氨基）异吲哚：用于对映选择性催化的一类高度模块化的钳形配体。
Angew Chem Int Ed Engl. 2008;47(25):4670-4. doi: 10.1002/anie.200801150.