A novel and unexpected aryne insertion cascade reaction on 2-arylidene-1,3-indandiones via conjugate addition of fluoride followed by formal C-C insertion is developed to afford dibenzo[a,d]cycloheptanoid derivatives in good yields with a single isomer. This reaction represents a rare instance of cyclic enone C-C bond insertion (acyl-alkenylation) in aryne chemistry. Interestingly, 2-arylidene-1,3-indandiones bearing electron rich functional groups provided dibenz[a,c]anthracene-9,14-dione derivatives via [4 + 2] cycloaddition followed by ring expansion.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/c9ob01900f | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Aryne Chemistry: Generation Methods and Reactions Incorporating Multiple Arynes.
Chem Rev
October 2024
Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
Article Synopsis
- Arynes are crucial for efficiently fusing (hetero)arenes with various substrates, helping create complex molecular structures useful in optoelectronic materials and bioactive compounds.
- The review covers methods and mechanisms for using multiple arynes in organic reactions, emphasizing the need for precise control to avoid unwanted side reactions.
- It categorizes aryne reactions and provides insights into the selection of aryne precursors, aiming to support advanced synthetic designs involving multiple arynes.
Fluoride-Mediated Aryne 1,2-Difunctionalization Involving C═S Bond Heterolysis.
J Org Chem
July 2024
Gansu International Scientific and Technological Cooperation Base of Water-Retention Chemical Functional Materials, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, Gansu, China.
We have successfully synthesized a series of bidentate ligands by utilizing 2-(trimethylsilyl)phenyl trifluorosulfonate as a precursor for the benzyl group. This method proceeded by inserting a polythiourea into the C═S π-bond, intramolecular ring proton migration, and ring opening. Salient features of this strategy are mild reaction conditions, a novel product structure, excellent stereochemistry, and a good functional group tolerance.
View Article and Find Full Text PDFHydrosilylation of Arynes with Silanes and Silicon-Based Polymer.
Chemistry
August 2024
Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, Guangdong Provincial Key Laboratory of Chiral Molecule and Drug Discovery, School of Chemistry, IGCME, Sun Yat-sen University, 510275, Guangzhou, Guangdong, China.
Benzyne derived from hexadehydrogenated Diels Alder (HDDA) reactions was found to be an efficient hydrosilylation acceptors. Various silanes can react smoothly with HDDA-derived benzyne to give the arylation products. Lewis acid such as boron trifluoride etherate can accelerate these hydrosilylation reactions.
View Article and Find Full Text PDFSwitchable chemoselective aryne reactions between nucleophiles and pericyclic reaction partners using either 3-methoxybenzyne or 3-silylbenzyne.
Nat Commun
April 2024
School of Chemistry and Chemical Engineering, Chongqing University, 174 Shazheng Street, Chongqing, 400030, PR China.
Arynes are known to serve as highly reactive benzene-based synthons, which have gained numerous successes in preparing functionalized arenes. Due to the superb electrophilic nature of these fleeting species, however, it is challenging to modulate the designated aryne transformation chemoselectively, when substrates possess multiple competing reaction sites. Here, we showcase our effort to manipulate chemoselective control between two major types of aryne transformations using either 3-methoxybenzyne or 3-silylbenzyne, where nucleophilic addition-triggered reactions and non-polar pericyclic reactions could be differentiated.
View Article and Find Full Text PDFAmino- and Alkoxybenziodoxoles: Facile Preparation and Use as Arynophiles.
Chemistry
May 2024
Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aoba, Aramaki, Aoba-ku, Sendai, 980-8578, Japan.
We report here on the facile synthesis of amino- and alkoxy-λ-iodanes supported by a benziodoxole (BX) template and their use as arynophiles. The amino- and alkoxy-BX derivatives can be readily synthesized by reacting the respective amines or alcohols with chlorobenziodoxole in the presence of a suitable base. Unlike previously known nitrogen- and oxygen-bound iodane compounds, which have primarily been employed as electrophilic group transfer agents or oxidants, the present amino- and alkoxy-BX reagents manifest themselves as nucleophilic amino and alkoxy transfer agents toward arynes.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!