• 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

利用酰基硅烷作为光功能导向基团的苯并环丁烯酮合成。

Benzocyclobutenone synthesis exploiting acylsilanes as photofunctional directing groups.

作者信息

Pilkington Rowan L, Ross Hannah J, Atkin Liselle, Priebbenow Daniel L

机构信息

Medicinal Chemistry Theme, Monash Institute of Pharmaceutical Sciences, Monash University Parkville VIC 3052 Australia

出版信息

Chem Sci. 2024 Oct 25;15(46):19328-35. doi: 10.1039/d4sc05715e.

DOI:10.1039/d4sc05715e
PMID:39502503
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11533050/
Abstract

The visible-light irradiation of acylsilane tethered vinyl ketones promotes an intramolecular Stetter-type reaction siloxycarbene intermediates. To exploit this unique mode of reactivity, we herein describe the innovative use of acylsilanes as photofunctional directing groups. First, an acylsilane directed ruthenium catalysed C-H olefination reaction was developed to generate benzoylsilanes bearing vinyl ketone functionality. Then, visible-light irradiation initiated the 1,4-conjugate addition of transient siloxycarbene intermediates with pendent vinyl ketones to afford unique benzocyclobutenone scaffolds primed for further synthetic elaboration.

摘要

酰基硅烷连接的乙烯基酮的可见光照射促进了分子内的施泰特型反应，生成硅氧基卡宾中间体。为了利用这种独特的反应模式，我们在此描述了酰基硅烷作为光功能导向基团的创新应用。首先，开发了一种酰基硅烷导向的钌催化的C-H烯基化反应，以生成具有乙烯基酮官能团的苯甲酰硅烷。然后，可见光照射引发了瞬态硅氧基卡宾中间体与侧链乙烯基酮的1,4-共轭加成，得到了独特的苯并环丁烯酮支架，为进一步的合成修饰做好了准备。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3cd0/11600531/c585bad90523/d4sc05715e-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3cd0/11600531/52122676298a/d4sc05715e-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3cd0/11600531/b0a072bfdea6/d4sc05715e-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3cd0/11600531/64a50e07eed7/d4sc05715e-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3cd0/11600531/c585bad90523/d4sc05715e-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3cd0/11600531/52122676298a/d4sc05715e-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3cd0/11600531/b0a072bfdea6/d4sc05715e-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3cd0/11600531/64a50e07eed7/d4sc05715e-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3cd0/11600531/c585bad90523/d4sc05715e-f3.jpg

相似文献

1
Benzocyclobutenone synthesis exploiting acylsilanes as photofunctional directing groups.利用酰基硅烷作为光功能导向基团的苯并环丁烯酮合成。
Chem Sci. 2024 Oct 25;15(46):19328-35. doi: 10.1039/d4sc05715e.
2
Acylsilanes in rhodium(III)-catalyzed directed aromatic C-H alkenylations and siloxycarbene reactions with C-C double bonds.铑(III)催化的导向芳基 C-H 烯基化反应和硅氧基卡宾与 C-C 双键的反应中的酰基硅烷。
Angew Chem Int Ed Engl. 2014 Jan 3;53(1):269-71. doi: 10.1002/anie.201307446. Epub 2013 Nov 19.
3
Visible-Light-Induced Catalyst-Free Carboxylation of Acylsilanes with Carbon Dioxide.可见光诱导的无催化剂酰基硅烷与二氧化碳的羧化反应
Org Lett. 2021 Mar 19;23(6):2303-2307. doi: 10.1021/acs.orglett.1c00435. Epub 2021 Mar 8.
4
Acylsilane Directed Rh-Catalyzed Arene C-H Alkylation with Maleimides and Visible-Light-Induced Siloxycarbene-Amide Cyclization: [3 + 2] Carbo-Annulation in Ru Catalysis.酰基硅烷导向的铑催化芳烃C-H与马来酰亚胺的烷基化反应以及可见光诱导的硅氧基卡宾-酰胺环化反应：钌催化中的[3 + 2]碳环化反应
Org Lett. 2023 Apr 21;25(15):2594-2599. doi: 10.1021/acs.orglett.3c00487. Epub 2023 Apr 10.
5
The thiazolium-catalyzed Sila-Stetter reaction: conjugate addition of acylsilanes to unsaturated esters and ketones.噻唑鎓催化的硅杂-施陶丁格反应：酰基硅烷对不饱和酯和酮的共轭加成。
J Am Chem Soc. 2004 Mar 3;126(8):2314-5. doi: 10.1021/ja0318380.
6
Visible-Light-Induced, Metal-Free Carbene Insertion into B-H Bonds between Acylsilanes and Pinacolborane.可见光诱导、无金属的卡宾插入酰基硅烷与频哪醇硼烷之间的B-H键反应
J Am Chem Soc. 2019 Oct 16;141(41):16227-16231. doi: 10.1021/jacs.9b08960. Epub 2019 Oct 1.
7
Visible-Light-Induced Siloxycarbene Addition to N═N of Azodicarboxylates: Synthesis of Acyl Hydrazides from Acylsilanes.可见光诱导的硅氧基卡宾加成到偶氮二甲酸酯的N═N上：从酰基硅烷合成酰肼。
Org Lett. 2024 Mar 15;26(10):2039-2044. doi: 10.1021/acs.orglett.4c00185. Epub 2024 Mar 4.
8
Stereoselective Synthesis of Silyl Enol Ethers with Acylsilanes and α,β-Unsaturated Ketones.用酰基硅烷和α,β-不饱和酮立体选择性合成硅基烯醇醚
Org Lett. 2024 Jul 19;26(28):5911-5916. doi: 10.1021/acs.orglett.4c01782. Epub 2024 Jul 8.
9
Visible-Light-Induced Generation of Fischer-Type Copper Carbene Complexes from Acylsilanes and Its Application to Catalytic [4 + 1] Cycloaddition with Siloxydienes.可见光诱导酰基硅烷生成费舍尔型卡宾铜配合物及其在与硅氧基二烯催化[4 + 1]环加成反应中的应用。
Org Lett. 2021 Dec 17;23(24):9490-9494. doi: 10.1021/acs.orglett.1c03683. Epub 2021 Nov 30.
10
Lewis Acid-Assisted Photoinduced Intermolecular Coupling between Acylsilanes and Aldehydes: A Formal Cross Benzoin-Type Condensation.路易斯酸辅助的酰基硅烷与醛之间的光致分子间偶联：一种形式上的交叉安息香型缩合反应。
Chemistry. 2018 Jan 12;24(3):543-546. doi: 10.1002/chem.201704776. Epub 2017 Nov 30.

本文引用的文献

1
Stereoselective Synthesis of Silyl Enol Ethers with Acylsilanes and α,β-Unsaturated Ketones.用酰基硅烷和α,β-不饱和酮立体选择性合成硅基烯醇醚
Org Lett. 2024 Jul 19;26(28):5911-5916. doi: 10.1021/acs.orglett.4c01782. Epub 2024 Jul 8.
2
Organocatalyzed Hydroacylation of Enones by Photosensitization of Acyl Silanes.通过酰基硅烷的光敏化实现烯酮的有机催化氢酰化反应
Chem Asian J. 2024 Jun 3;19(11):e202400240. doi: 10.1002/asia.202400240. Epub 2024 May 14.
3
Synthesis of silyl indenes by ruthenium-catalyzed aldehyde- and acylsilane-enabled C-H alkylation/cyclization.
通过钌催化的醛和酰基硅烷参与的C-H烷基化/环化反应合成硅基茚。
Org Biomol Chem. 2024 Jan 17;22(3):466-471. doi: 10.1039/d3ob01699d.
4
Acylsilanes in Transition-Metal-Catalyzed and Photochemical Reactions: Clarifying Product Formation.过渡金属催化和光化学反应中的酰基硅烷：阐明产物形成过程
J Org Chem. 2023 Oct 6;88(19):14205-14209. doi: 10.1021/acs.joc.3c01454. Epub 2023 Sep 22.
5
The Corey-Seebach Reagent in the 21st Century: A Review.《21 世纪的 Corey-Seebach 试剂：综述》。
Molecules. 2023 May 26;28(11):4367. doi: 10.3390/molecules28114367.
6
Transition-Metal-Catalyzed C-H Bond Activation for the Formation of C-C Bonds in Complex Molecules.过渡金属催化的 C-H 键活化在复杂分子中 C-C 键的形成。
Chem Rev. 2023 Jun 28;123(12):7692-7760. doi: 10.1021/acs.chemrev.2c00888. Epub 2023 May 10.
7
An HFIP-assisted, cobalt-catalyzed three-component electrophilic C-H amination/cyclization/directing group removal cascade to naphtho[1,2-d]imidazoles.HFIP 辅助的钴催化三组分亲电 C-H 胺化/环化/导向基团消除级联反应构建萘并[1,2-d]咪唑。
Chem Commun (Camb). 2023 May 4;59(37):5595-5598. doi: 10.1039/d3cc00749a.
8
Acylsilane Directed Rh-Catalyzed Arene C-H Alkylation with Maleimides and Visible-Light-Induced Siloxycarbene-Amide Cyclization: [3 + 2] Carbo-Annulation in Ru Catalysis.酰基硅烷导向的铑催化芳烃C-H与马来酰亚胺的烷基化反应以及可见光诱导的硅氧基卡宾-酰胺环化反应：钌催化中的[3 + 2]碳环化反应
Org Lett. 2023 Apr 21;25(15):2594-2599. doi: 10.1021/acs.orglett.3c00487. Epub 2023 Apr 10.
9
The Indenyl Effect: Accelerated C-H Amidation of Arenes via Ind*Rh Nitrene Transfer Catalysis.茚基效应：通过*Ind-Rh 氮宾转移催化加速芳基的 C-H 酰胺化反应。
Angew Chem Int Ed Engl. 2023 Jun 5;62(23):e202302175. doi: 10.1002/anie.202302175. Epub 2023 Apr 28.
10
Palladium-catalyzed addition of acylsilanes across alkynes the activation of a C-Si bond.钯催化酰基硅烷与炔烃的加成反应：C-Si键的活化
Chem Sci. 2023 Feb 13;14(10):2706-2712. doi: 10.1039/d3sc00181d. eCollection 2023 Mar 8.