• 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

手性仲烷基铜物种烯丙基化反应的最新进展。

Recent advances in allylation of chiral secondary alkylcopper species.

作者信息

Kim Minjae, Kim Gwanggyun, Kim Doyoon, Lee Jun Hee, Cho Seung Hwan

机构信息

Department of Chemistry, Pohang University of Science and Technology (POSTECH), Pohang, 37673, Republic of Korea.

Department of Advanced Materials Chemistry, Dongguk University WISE, Gyeongju 38066, Republic of Korea.

出版信息

Beilstein J Org Chem. 2025 Mar 20;21:639-658. doi: 10.3762/bjoc.21.51. eCollection 2025.

DOI:10.3762/bjoc.21.51
PMID:40130179
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11931642/
Abstract

The transition-metal-catalyzed asymmetric allylic substitution represents a pivotal methodology in organic synthesis, providing remarkable versatility for complex molecule construction. Particularly, the generation and utilization of chiral secondary alkylcopper species have received considerable attention due to their unique properties in stereoselective allylic substitution. This review highlights recent advances in copper-catalyzed asymmetric allylic substitution reactions with chiral secondary alkylcopper species, encompassing several key strategies for their generation: stereospecific transmetalation of organolithium and organoboron compounds, copper hydride catalysis, and enantiotopic-group-selective transformations of 1,1-diborylalkanes. Detailed mechanistic insights into stereochemical control and current challenges in this field are also discussed.

摘要

过渡金属催化的不对称烯丙基取代是有机合成中的关键方法，为复杂分子构建提供了显著的通用性。特别是，手性仲烷基铜物种的生成和利用因其在立体选择性烯丙基取代中的独特性质而受到了广泛关注。本文综述了铜催化的手性仲烷基铜物种不对称烯丙基取代反应的最新进展，包括其生成的几种关键策略：有机锂和有机硼化合物的立体专一性转金属化、氢化铜催化以及1,1-二硼基烷烃的对映异位基团选择性转化。还讨论了该领域立体化学控制的详细机理见解和当前挑战。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/bc91da637d06/Beilstein_J_Org_Chem-21-639-g020.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/bb1ee83a6d92/Beilstein_J_Org_Chem-21-639-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/c0e10b31f0a5/Beilstein_J_Org_Chem-21-639-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/c921ad483bdb/Beilstein_J_Org_Chem-21-639-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/e83c2b8d3f08/Beilstein_J_Org_Chem-21-639-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/e8b7187c64ee/Beilstein_J_Org_Chem-21-639-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/d77f7f856eda/Beilstein_J_Org_Chem-21-639-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/b41a4dfc1878/Beilstein_J_Org_Chem-21-639-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/82681b0ad2c6/Beilstein_J_Org_Chem-21-639-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/51293fe1bf72/Beilstein_J_Org_Chem-21-639-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/b3078a4d0e39/Beilstein_J_Org_Chem-21-639-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/2dc451118e77/Beilstein_J_Org_Chem-21-639-g012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/95db37b5ea88/Beilstein_J_Org_Chem-21-639-g013.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/0cb9d9da0c74/Beilstein_J_Org_Chem-21-639-g014.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/5d27e62490fb/Beilstein_J_Org_Chem-21-639-g015.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/4ad4354b21ab/Beilstein_J_Org_Chem-21-639-g016.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/8886fe9f697f/Beilstein_J_Org_Chem-21-639-g017.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/54a8c805b3bb/Beilstein_J_Org_Chem-21-639-g018.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/40bbfa5034c9/Beilstein_J_Org_Chem-21-639-g019.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/bc91da637d06/Beilstein_J_Org_Chem-21-639-g020.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/bb1ee83a6d92/Beilstein_J_Org_Chem-21-639-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/c0e10b31f0a5/Beilstein_J_Org_Chem-21-639-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/c921ad483bdb/Beilstein_J_Org_Chem-21-639-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/e83c2b8d3f08/Beilstein_J_Org_Chem-21-639-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/e8b7187c64ee/Beilstein_J_Org_Chem-21-639-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/d77f7f856eda/Beilstein_J_Org_Chem-21-639-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/b41a4dfc1878/Beilstein_J_Org_Chem-21-639-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/82681b0ad2c6/Beilstein_J_Org_Chem-21-639-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/51293fe1bf72/Beilstein_J_Org_Chem-21-639-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/b3078a4d0e39/Beilstein_J_Org_Chem-21-639-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/2dc451118e77/Beilstein_J_Org_Chem-21-639-g012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/95db37b5ea88/Beilstein_J_Org_Chem-21-639-g013.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/0cb9d9da0c74/Beilstein_J_Org_Chem-21-639-g014.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/5d27e62490fb/Beilstein_J_Org_Chem-21-639-g015.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/4ad4354b21ab/Beilstein_J_Org_Chem-21-639-g016.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/8886fe9f697f/Beilstein_J_Org_Chem-21-639-g017.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/54a8c805b3bb/Beilstein_J_Org_Chem-21-639-g018.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/40bbfa5034c9/Beilstein_J_Org_Chem-21-639-g019.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/de8a/11931642/bc91da637d06/Beilstein_J_Org_Chem-21-639-g020.jpg

相似文献

1
Recent advances in allylation of chiral secondary alkylcopper species.手性仲烷基铜物种烯丙基化反应的最新进展。
Beilstein J Org Chem. 2025 Mar 20;21:639-658. doi: 10.3762/bjoc.21.51. eCollection 2025.
2
Catalytic Chemo- and Enantioselective Transformations of -Diborylalkanes and (Diborylmethyl)metallic Species.-二硼烷基烷烃和（二硼甲基）金属物种的催化手性化学和对映选择性转化。
Acc Chem Res. 2021 Oct 19;54(20):3917-3929. doi: 10.1021/acs.accounts.1c00455. Epub 2021 Oct 6.
3
Direct Stereoconvergent Allylation of Chiral Alkylcopper Nucleophiles with Racemic Allylic Phosphates.手性烷基铜亲核试剂与外消旋烯丙基磷酸酯的直接对映选择性 allylation。
Chemistry. 2020 Feb 26;26(12):2592-2596. doi: 10.1002/chem.201905361. Epub 2020 Feb 21.
4
Regio- and Stereoselective Allylic Substitutions of Chiral Secondary Alkylcopper Reagents: Total Synthesis of (+)-Lasiol, (+)-13-Norfaranal, and (+)-Faranal.手性仲烷基铜试剂的区域和立体选择性烯丙基取代反应：(+)-拉西奥、(+)-13-去甲法呢醛和(+)-法呢醛的全合成。
Angew Chem Int Ed Engl. 2019 Jan 28;58(5):1509-1514. doi: 10.1002/anie.201811330. Epub 2018 Dec 28.
5
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.
6
Copper-catalyzed yne-allylic substitutions: concept and recent developments.铜催化的炔烃-烯丙基取代反应：概念与最新进展
Beilstein J Org Chem. 2024 Oct 31;20:2739-2775. doi: 10.3762/bjoc.20.232. eCollection 2024.
7
Copper-Catalyzed Enantiotopic-Group-Selective Allylation of -Diborylalkanes.铜催化的对映选择性-二硼烷基烷烃的亲核加成反应。
J Am Chem Soc. 2021 Jan 20;143(2):1069-1077. doi: 10.1021/jacs.0c11750. Epub 2021 Jan 4.
8
Asymmetric Rhodium-Catalyzed Allylic Substitution Reactions: Discovery, Development and Applications to Target-Directed Synthesis.不对称铑催化烯丙基取代反应：发现、发展及在靶向合成中的应用。
J Org Chem. 2018 Oct 5;83(19):11463-11479. doi: 10.1021/acs.joc.8b00583. Epub 2018 Sep 5.
9
Photocatalysis Meets Copper Catalysis: A New Opportunity for Asymmetric Multicomponent Radical Cross-Coupling Reactions.光催化与铜催化的结合：不对称多组分自由基交叉偶联反应的新机遇
Acc Chem Res. 2024 Dec 3;57(23):3433-3448. doi: 10.1021/acs.accounts.4c00638. Epub 2024 Nov 13.
10
Copper-Catalyzed γ-Selective and Stereospecific Allylic Cross-Coupling with Secondary Alkylboranes.铜催化的与仲烷基硼烷的γ-选择性和立体特异性烯丙基交叉偶联反应。
Chemistry. 2015 Jun 26;21(27):9666-70. doi: 10.1002/chem.201501055. Epub 2015 May 26.

引用本文的文献

1
Copper catalysis: a constantly evolving field.铜催化：一个不断发展的领域。
Beilstein J Org Chem. 2025 Jul 17;21:1477-1479. doi: 10.3762/bjoc.21.109. eCollection 2025.

本文引用的文献

1
Copper-Catalyzed Regio-, Diastereo-, and Enantioselective Allylic Alkylation with 1,1-Diborylalkanes.铜催化的1,1-二硼基烷烃的区域、非对映体和对映体选择性烯丙基烷基化反应
J Am Chem Soc. 2024 Dec 18;146(50):34861-34869. doi: 10.1021/jacs.4c14150. Epub 2024 Dec 6.
2
Copper-Catalyzed Regiodivergent Asymmetric Difunctionalization of Terminal Alkynes.铜催化末端炔烃的区域发散性不对称双官能化反应
Angew Chem Int Ed Engl. 2024 Oct 21;63(43):e202410833. doi: 10.1002/anie.202410833. Epub 2024 Aug 19.
3
Substrate Plasticity Enables Group-Selective Transmetalation: Catalytic Stereospecific Cross-Couplings of Tertiary Boronic Esters.
底物可塑性实现基团选择性转金属化：叔硼酸酯的催化立体专一性交叉偶联反应
J Am Chem Soc. 2023 Sep 27;145(38):20755-20760. doi: 10.1021/jacs.3c07129. Epub 2023 Aug 31.
4
Copper-Catalyzed Stereospecific Transformations of Alkylboronic Esters.铜催化的烷基硼酸酯的立体特异性转化。
J Am Chem Soc. 2022 Jul 6;144(26):11546-11552. doi: 10.1021/jacs.2c04037. Epub 2022 Jun 23.
5
Catalytic Chemo- and Enantioselective Transformations of -Diborylalkanes and (Diborylmethyl)metallic Species.-二硼烷基烷烃和（二硼甲基）金属物种的催化手性化学和对映选择性转化。
Acc Chem Res. 2021 Oct 19;54(20):3917-3929. doi: 10.1021/acs.accounts.1c00455. Epub 2021 Oct 6.
6
Copper-Catalyzed Enantiotopic-Group-Selective Allylation of -Diborylalkanes.铜催化的对映选择性-二硼烷基烷烃的亲核加成反应。
J Am Chem Soc. 2021 Jan 20;143(2):1069-1077. doi: 10.1021/jacs.0c11750. Epub 2021 Jan 4.
7
CuH-Catalyzed Olefin Functionalization: From Hydroamination to Carbonyl Addition.CuH 催化的烯烃官能化：从氨氢化反应到羰基加成反应。
Acc Chem Res. 2020 Jun 16;53(6):1229-1243. doi: 10.1021/acs.accounts.0c00164. Epub 2020 May 13.
8
Sulfonate N-Heterocyclic Carbene-Copper Complexes: Uniquely Effective Catalysts for Enantioselective Synthesis of C-C, C-B, C-H, and C-Si Bonds.磺酸酯 N-杂环卡宾-铜配合物：手性合成 C-C、C-B、C-H 和 C-Si 键的高效独特催化剂。
Angew Chem Int Ed Engl. 2020 Nov 23;59(48):21304-21359. doi: 10.1002/anie.202003755. Epub 2020 Aug 26.
9
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.
10
Regio- and Stereoselective Allylic Substitutions of Chiral Secondary Alkylcopper Reagents: Total Synthesis of (+)-Lasiol, (+)-13-Norfaranal, and (+)-Faranal.手性仲烷基铜试剂的区域和立体选择性烯丙基取代反应：(+)-拉西奥、(+)-13-去甲法呢醛和(+)-法呢醛的全合成。
Angew Chem Int Ed Engl. 2019 Jan 28;58(5):1509-1514. doi: 10.1002/anie.201811330. Epub 2018 Dec 28.