文献检索文档翻译深度研究
Suppr Zotero 插件Zotero 插件
邀请有礼套餐&价格历史记录

新学期,新优惠

限时优惠:9月1日-9月22日

30天高级会员仅需29元

1天体验卡首发特惠仅需5.99元

了解详情
不再提醒
插件&应用
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
高级版
套餐订阅购买积分包
AI 工具
文献检索文档翻译深度研究
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 @ 2025

通过光氧化还原协同 NHC/钯催化,从醛到酮的烷基 C(sp)-H 功能化。

Ketones from aldehydes via alkyl C(sp)-H functionalization under photoredox cooperative NHC/palladium catalysis.

机构信息

Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, 100190, Beijing, China.

University of Chinese Academy of Sciences, 100049, Beijing, China.

出版信息

Nat Commun. 2023 Jul 8;14(1):4044. doi: 10.1038/s41467-023-39707-8.


DOI:10.1038/s41467-023-39707-8
PMID:37422483
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10329650/
Abstract

Direct synthesis of ketones from aldehydes features high atom- and step-economy. Yet, the coupling of aldehydes with unactivated alkyl C(sp)-H remains challenging. Herein, we develop the synthesis of ketones from aldehydes via alkyl C(sp)-H functionalization under photoredox cooperative NHC/Pd catalysis. The two-component reaction of iodomethylsilyl alkyl ether with aldehydes gave a variety of β-, γ- and δ-silyloxylketones via 1,n-HAT (n = 5, 6, 7) of silylmethyl radicals to generate secondary or tertiary alkyl radicals and following coupling with ketyl radicals from aldehydes under photoredox NHC catalysis. The three-component reaction with the addition of styrenes gave the corresponding ε-hydroxylketones via the generation of benzylic radicals by the addition of alkyl radicals to styrenes and following coupling with ketyl radicals. This work demonstrates the generation of ketyl radical and alkyl radical under the photoredox cooperative NHC/Pd catalysis, and provides two and three component reactions for the synthesis of ketones from aldehydes with alkyl C(sp)-H functionalization. The synthetic potential of this protocol was also further illustrated by the late-stage functionalization of natural products.

摘要

醛与未活化的烷基 C(sp)-H 的偶联仍然具有挑战性。在此,我们通过光氧化还原协同 NHC/Pd 催化发展了醛通过烷基 C(sp)-H 官能化来合成酮。碘甲基硅烷基醚与醛的二组分反应通过硅甲基自由基的 1,n-HAT(n=5,6,7)生成仲或叔烷基自由基,并在光氧化还原 NHC 催化下与醛的酮基自由基偶联,生成各种β-、γ-和δ-硅氧代酮。通过添加苯乙烯的三组分反应,通过烷基自由基加成到苯乙烯中生成苄基自由基,并与醛的酮基自由基偶联,生成相应的ε-羟基酮。这项工作证明了在光氧化还原协同 NHC/Pd 催化下可以生成酮基自由基和烷基自由基,并提供了两种和三种组分反应,用于通过烷基 C(sp)-H 官能化从醛合成酮。该方案的合成潜力也通过天然产物的后期官能化进一步得到了说明。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f1e0/10329650/7990a97b398a/41467_2023_39707_Fig6_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f1e0/10329650/c9d323bf5f5d/41467_2023_39707_Fig1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f1e0/10329650/a642a0c14400/41467_2023_39707_Fig2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f1e0/10329650/a3e92fc01e8f/41467_2023_39707_Fig3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f1e0/10329650/b33203764b46/41467_2023_39707_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f1e0/10329650/c843f6753b6e/41467_2023_39707_Fig5_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f1e0/10329650/7990a97b398a/41467_2023_39707_Fig6_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f1e0/10329650/c9d323bf5f5d/41467_2023_39707_Fig1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f1e0/10329650/a642a0c14400/41467_2023_39707_Fig2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f1e0/10329650/a3e92fc01e8f/41467_2023_39707_Fig3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f1e0/10329650/b33203764b46/41467_2023_39707_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f1e0/10329650/c843f6753b6e/41467_2023_39707_Fig5_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f1e0/10329650/7990a97b398a/41467_2023_39707_Fig6_HTML.jpg

相似文献

[1]
Ketones from aldehydes via alkyl C(sp)-H functionalization under photoredox cooperative NHC/palladium catalysis.

Nat Commun. 2023-7-8

[2]
Cooperative NHC and Photoredox Catalysis for the Synthesis of β-Trifluoromethylated Alkyl Aryl Ketones.

Angew Chem Int Ed Engl. 2020-11-2

[3]
Synthetic and Mechanistic Implications of Chlorine Photoelimination in Nickel/Photoredox C(sp)-H Cross-Coupling.

Acc Chem Res. 2021-2-16

[4]
Photoredox cooperative N-heterocyclic carbene/palladium-catalysed alkylacylation of alkenes.

Nat Commun. 2022-9-30

[5]
Direct Hydroxylarylation of Benzylic Carbons (sp/sp/sp) via Radical-Radical Cross-Coupling Powered by Paired Electrolysis.

J Org Chem. 2023-1-6

[6]
Formal β-C-H Arylation of Aldehydes and Ketones by Cooperative Nickel and Photoredox Catalysis.

Angew Chem Int Ed Engl. 2022-8-1

[7]
Cooperative NHC and Photoredox Catalysis for the Synthesis of 1,4-Dicarbonyl Compounds via Diacylation of Alkenes.

Org Lett. 2022-8-12

[8]
Direct β-functionalization of cyclic ketones with aryl ketones via the merger of photoredox and organocatalysis.

J Am Chem Soc. 2013-11-22

[9]
Photoredox activation for the direct β-arylation of ketones and aldehydes.

Science. 2013-3-29

[10]
Carbene-Catalyzed Intermolecular Dehydrogenative Coupling of Aldehydes with C(sp )-H Bonds.

Angew Chem Int Ed Engl. 2023-6-5

引用本文的文献

[1]
Deconstructive Radical-Radical Coupling for Programmable Remote Acylation.

Angew Chem Int Ed Engl. 2025-8-25

[2]
-Heterocyclic carbene catalytic 1,2-boron migrative acylation accelerated by photocatalysis.

Sci Adv. 2024-7-26

本文引用的文献

[1]
Recent advances in the chemistry and applications of N-heterocyclic carbenes.

Nat Rev Chem. 2021-10

[2]
Diastereoselective Radical Aminoacylation of Olefins through N-Heterocyclic Carbene Catalysis.

J Am Chem Soc. 2022-12-14

[3]
Photoredox cooperative N-heterocyclic carbene/palladium-catalysed alkylacylation of alkenes.

Nat Commun. 2022-9-30

[4]
Synthesis of β-Thiolated-α-arylated Ketones Enabled by Photoredox and -Heterocyclic Carbene-Catalyzed Radical Relay of Alkenes with Disulfides and Aldehydes.

Org Lett. 2022-8-5

[5]
Carbene and photocatalyst-catalyzed decarboxylative radical coupling of carboxylic acids and acyl imidazoles to form ketones.

Nat Commun. 2022-5-23

[6]
Three-Component Visible-Light-Induced Palladium-Catalyzed 1,2-Alkyl Carbamoylation/Cyanation of Alkenes.

ACS Catal. 2021-11-5

[7]
Aroyl Fluorides as Bifunctional Reagents for Dearomatizing Fluoroaroylation of Benzofurans.

J Am Chem Soc. 2022-4-27

[8]
Catalytic Desymmetric Dicarbofunctionalization of Unactivated Alkenes.

Angew Chem Int Ed Engl. 2022-6-27

[9]
Remote C(sp )-H Acylation of Amides and Cascade Cyclization via N-Heterocyclic Carbene Organocatalysis.

Angew Chem Int Ed Engl. 2022-4-4

[10]
Polyethylene materials with in-chain ketones from nonalternating catalytic copolymerization.

Science. 2021-10-29

文献AI研究员

20分钟写一篇综述,助力文献阅读效率提升50倍

立即体验

用中文搜PubMed

大模型驱动的PubMed中文搜索引擎

马上搜索

推荐工具

医学文档翻译智能文献检索