A facile synthesis of cyclopropenes and fluorinated cyclopropanes from readily available alkyl triflones was developed. The reaction, regardless of electronic effect, gave products in good to excellent yields and moderate diastereoselectivity. The mechanism may involve tandem Michael addition of triflones/intramolecular nucleophilic cyclization (elimination of -SO CF )/elimination of fluoride.
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http://dx.doi.org/10.1002/chem.202104364 | DOI Listing |
J Am Chem Soc
January 2025
Frontiers Science Center for Transformative Molecules, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China.
Direct synthesis of enantioenriched scaffolds with multiple adjacent stereocenters remains an important yet challenging task. Herein, we describe a highly diastereo- and enantioselective Cu-catalyzed alkylboration of cyclopropenes, with less reactive alkyl iodides as electrophiles, for the efficient synthesis of -substituted borylated cyclopropanes bearing three consecutive stereocenters. This protocol features mild conditions, a broad substrate scope, and good functional group tolerance, affording an array of chiral borylated cyclopropanes in good to high yields with excellent diastereo- and enantioselectivities.
View Article and Find Full Text PDFOrg Lett
January 2025
Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, P. R. China.
Sulfone motifs play important roles in bioactive compounds and functional materials. The development of efficient methodologies for constructing sulfonyl-containing compounds has thus attracted considerable attention. Here, we introduce a protocol for the preparation of alkyl aryl sulfones under mild conditions.
View Article and Find Full Text PDFOrg Lett
January 2025
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
Angew Chem Int Ed Engl
December 2024
School of Chemistry and Chemical Engineering, Key Laboratory of Colloid and Interface Chemistry of the Ministry of Education, Shandong University, Jinan, 250100, P. R. China.
Catalytic transformation of carbene species constitutes a fundamental part in organic synthesis, and the research in this direction has been dominated by transition metals while organic catalysts are difficult to mimic such transition-metal-like reactivity. It would significantly advance carbene chemistry if organic catalysts enable achieving classical metal-carbene approaches otherwise unrealizable reactions. Herein, we report that chalcogen bonding catalysis can solve reactivity problem to achieve an elusive Buchner ring expansion of aryl ketones appending a cyclopropene moiety as carbene precursor.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan.
A low-valent niobium species generated from NbCl and 1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene (-Me-CHD) in combination with PPh catalyzed a [2+2+1]-cycloaddition reaction of 3,3-disubstituted cyclopropenes and 2 equiv of diaryl/dialkylalkynes, leading to isomeric mixtures of multisubstituted cyclopentadienes -. The initial catalyst activation process was a one-electron reduction of NbCl with -Me-CHD to provide [NbCl(μ-Cl) (L)] (L = PMePh (), L = PPh ()) in the presence of phosphine ligands. An NMR spectroscopic time course experiment using complex as the catalyst revealed an induction period for the product formation, corresponding to an additional one-electron reduction of by the substrates to give catalytically active η-alkyne complexes of NbCl.
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