98%
921
2 minutes
20
An efficient and expedient fluoride-mediated α-selective 1,6-conjugate addition of allenic esters to para-quinone methides has been developed. The reaction exhibited an excellent substrate scope, and a wide range of α-diarylmethylated allenic esters were obtained in good to excellent yields. It was further shown that the strategy could be extended to isatin-derived quinone methides yielding allenic esters containing 3,3-disubstituted oxindoles. The tert-butyl ester of α-diarylmethylated allenoate was effectively converted into γ-butenolide through a Au/Ag catalyzed cyclization strategy.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/acs.joc.8b01074 | DOI Listing |
Nat Commun
May 2025
INSA Rouen Normandie, Univ. Rouen Normandie, CNRS, Normandie Univ., Institut CARMeN UMR 6064, F-76000, Rouen, France.
Allenyl silanes and boronates are pivotal building blocks in organic synthesis. Nevertheless, their synthesis requires the manipulation of transition metal or highly reactive species. Hence, the development of more sustainable protocol is highly sought after.
View Article and Find Full Text PDFSci Adv
May 2025
Department of Laboratory Medicine, Zhongnan Hospital of Wuhan University, Engineering Research Center of Organosilicon Compounds and Materials (Ministry of Education), Hubei Key Lab on Organic and Polymeric OptoElectronic Materials, College of Chemistry and Molecular Sciences, The Institute for Adva
Cross-electrophile coupling (XEC) is a powerful strategy for forming C-C bonds in synthetic organic chemistry. While XEC reactions between two electrophiles are well established, those involving three distinct electrophiles have remained underdeveloped. Herein, we report an intriguing formal triple XEC enabled by palladium/norbornene cooperative catalysis.
View Article and Find Full Text PDFOrg Lett
April 2025
Department of Chemistry and Biochemistry, Baylor University, Waco, Texas 76706, United States.
Though precedent remains limited, the selective interhalogenation of allenes offers a valuable synthetic strategy to access products where each halide exhibits orthogonal reactivity. Here, we describe a Lewis base-catalyzed approach for the dihalogenation (bromochlorination, iodochlorination, iodobromination, and dibromination) of terminal allenes. By employing just 1 mol % of triphenylphosphine oxide or hexamethylphosphoramide to activate thionyl halides in the presence of electrophilic halogenation reagents, we achieve the conversion of monosubstituted allenes to vicinal allylic, vinylic dihalides with up to 93% yield and >20:1 regioisomeric ratio, favoring the branched dihalogenated product.
View Article and Find Full Text PDFOrg Lett
March 2025
School of Chemistry & Materials Science, Jiangsu Normal University, Xuzhou 221116, China.
Instead of the conventional [4+2] cycloaddition, a regioselective Schmittel-type [2+2] cycloaddition of yne-allene esters, generated from copper-catalyzed dediazotized coupling of γ-alkynyl diazoacetates with terminal alkynes, is reported, enabling a bicyclization process to produce a diverse array of C-arylated cyclobuta[]indenes in moderate to good yields. The protocol features wide functional group compatibility, mild reaction conditions, and experimental simplicity, holding significant potential for building new tricyclic cyclobutenes.
View Article and Find Full Text PDFChem Sci
December 2024
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology Guangzhou 510640 China
Transition metal-catalyzed 1,3-acyloxy migration of propargylic esters represents one of the most straightforward routes to access allene intermediates, which could engage in various fascinating subsequent transformations. However, this process is often limited to propargylic esters with electron-donating groups due to intrinsic electronic bias, and the subsequent intermolecular reactions are quite limited. Herein, we disclosed an unprecedented Rh(ii)-catalyzed 1,3-acyloxy migration of electron-deficient propargylic esters, followed by intermolecular [2 + 2] cycloaddition with readily available alkenes and alkynes, and a large array of valuable alkylidenecyclobutane/ene scaffolds could be obtained facilely in one pot.
View Article and Find Full Text PDF