A novel gold (I)-catalyzed synthetic strategy has been achieved for an efficient construction of indenylidene derivatives from substituted 1,6-diynes. This reaction describes the unique reactivity of gold catalysis in facilitating the intramolecular [3,3]-sigmatropic rearrangement, 5-exo dig cyclization followed by 1,5-migration of acryl group, resulting in the formation of substituted indenylidenes. Various substituted indenylidenes were successfully synthesized with up to 92 % yields. In this protocol, two new C-C bonds were sequentially formed atom economically in one pot.
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http://dx.doi.org/10.1002/asia.202400310 | DOI Listing |
Chem Asian J
July 2024
Centre for X-ray Crystallography, CSIR-Indian Institute of Chemical Technology, 500007, Hyderabad, India.
A novel gold (I)-catalyzed synthetic strategy has been achieved for an efficient construction of indenylidene derivatives from substituted 1,6-diynes. This reaction describes the unique reactivity of gold catalysis in facilitating the intramolecular [3,3]-sigmatropic rearrangement, 5-exo dig cyclization followed by 1,5-migration of acryl group, resulting in the formation of substituted indenylidenes. Various substituted indenylidenes were successfully synthesized with up to 92 % yields.
View Article and Find Full Text PDFSci Rep
July 2022
Department of Chemistry, Faculty of Science, Imam Khomeini International University, Qazvin, Iran.
A new multi-component reaction for the synthesis of novel and diverse spiro-imidazo pyridine-indene derivatives named spiro[imidazo[1,2-a]indeno[2,1-e]pyridine-5,1'-indene and indenylidene-1H-spiro[imidazo[1,2-a]pyridine-7,1'-indene was successfully developed by the reaction between heterocyclic ketene aminals (generated from 1,1-bis(methylthio)-2-nitro ethylene and diamine) and [1,2'-biindenylidene]-1',3,3'-trione (bindone) (in situ generated from self-condensation of 1,3-indandion) by using malononitrile as a promoter or as one of the precursors respectively in the presence of p-TSA as the acid catalyst in EtOH as reaction medium under reflux conditions. Depending on whether the reaction is single-step or two-step, malononitrile can act as a promoter or reactant. The convenient one-pot operation, straightforward isolation without using additional purification methods, and the use of a variety of diamines and cysteamine hydrochloride causing a variety of structural products are attractive aspects of the present approach.
View Article and Find Full Text PDFOrganometallics
May 2021
Departamento de Química Inorgánica - Instituto de Síntesis Química y Catálisis Homogénea (ISQCH) - Centro de Innovación en Química Avanzada (ORFEO-CINCA), Universidad de Zaragoza - CSIC, 50009 Zaragoza, Spain.
An unusual 1,3-hydrogen shift from the metal center to the C atom of the C-chain of the allenylidene ligand in a hydride-osmium(II)-allenylidene complex is the beginning of several interesting transformations in the cumulene. The hydride-osmium(II)-allenylidene complex was prepared in two steps, starting from the tetrahydride dimer [(Os(H···H){κ-,,-[xant(P Pr)]})(μ-Cl)][BF] (). Complex reacts with 1,1-diphenyl-2-propyn-1-ol to give the hydride-osmium(II)-alkenylcarbyne [OsHCl(≡CCH=CPh){κ-,,-[xant(P Pr)]}]BF (), which yields OsHCl(=C=C=CPh){κ-,,-[xant(P Pr)]} () by selective abstraction of the C-H hydrogen atom of the alkenylcarbyne ligand with K BuO.
View Article and Find Full Text PDFOrg Biomol Chem
April 2021
Fluoro and Agrochemicals Department, CSIR-Indian Institute of Chemical Technology, Hyderabad, 500007, India. and Academy of Scientific and Innovative Research, Ghaziabad, 201002, India.
An efficient gold-catalyzed formation of indenylidene-derived 1H-isochromene-4-carbaldehydes from substituted 1,5,10-triyne-O-silanes was developed under mild reaction conditions. In this reaction, gold-catalyzed selective oxidation, 1,2-migration, nucleophilic addition and then 5-endo-dig cyclization took place regioselectively. The indenylidene-derived isochromene-4-carbaldehydes were synthesized in moderate to very good yields via the formation of new C-C and C-O bonds in one pot.
View Article and Find Full Text PDFJ Am Chem Soc
July 2019
Center for Catalysis Research and Innovation, and Department of Chemistry and Biomolecular Sciences , University of Ottawa, Ottawa , Ontario K1N 6N5 , Canada.
Access to leading olefin metathesis catalysts, including the Grubbs, Hoveyda, and Grela catalysts, ultimately rests on the nonscaleable transfer of a benzylidene ligand from an unstable, impure aryldiazomethane. The indenylidene ligand can be reliably installed, but to date yields much less reactive catalysts. A fast-initiating, dimeric indenylidene complex () is reported, which reconciles high activity with scaleable synthesis.
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