The first formal [3 + 2] cycloaddition reaction of in situ generated azaoxyallyl cation with cyclic ketones has been developed using mild reaction conditions. A variety of spiro-4-oxazolidinones was obtained in excellent yields (up to 99%). The high efficiency of this process, coupled with the operational simplicity, makes it an attractive method for the synthesis of spiro-4-oxazolidinones.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/acs.joc.7b01728 | DOI Listing |
RSC Adv
January 2025
Department of Organic Chemistry, University of Debrecen Egyetem Square 1 Debrecen 4032 Hungary
Domino Knoevenagel-cyclization reactions of styrene substrates, containing an -(-formyl)aryl subunit, were carried out with -substituted 2-cyanoacetamides to prepare tetrahydro-4-pyrano[3,4-]quinolone and hexahydrobenzo[]phenanthridine derivatives by competing IMHDA and IMSDA cyclization, respectively. The diastereoselective IMHDA step with α,β-unsaturated amide, thioamide, ester and ketone subunits as a heterodiene produced condensed chiral tetrahydropyran or thiopyran derivatives, which in the case of Meldrum's acid were reacted further with amine nucleophiles in a multistep domino sequence. In order to simplify the benzene-condensed tricyclic core of the targets and get access to hexahydro-1-pyrano[3,4-]pyridine derivatives, a truncated substrate was reacted with cyclic and acyclic active methylene reagents in diastereoselective Knoevenagel-IMHDA reactions to prepare novel condensed heterocyclic scaffolds.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Frontiers Science Center for New Organic Matter, Nankai University, Tianjin, 300071, P. R. China.
Reliable methods for rapidly constructing C(sp)-rich three-dimensional polycycles are in high demand for organic synthesis and medicinal chemistry. Although there are various mature systems for synthesizing five- or six-membered polycycles, a catalytic platform for accessing diverse cycloheptanoid-containing polycyclic scaffolds is lacking. Herein, we describe a method for copper-catalyzed intramolecular 2-aminoallyl cation-diene (4+3) cycloaddition reactions.
View Article and Find Full Text PDFTetrahedron
February 2025
Department of Chemistry, Western Washington University, Bellingham, WA 98225 (USA).
Beta-hydroxy ketones can be reduced using a sequence of ruthenium-catalyzed silyl etherification followed by tetrabutylammonium fluoride (TBAF) promoted intramolecular hydrosilylation. Switching from TBAF to tetrabutylammonium difluorotriphenylsilicate (TBAT), even without first forming the silyl ether, gave cyclic dioxasilinane products. These somewhat sensitive compounds could be isolated pure by column chromatography using florisil as the stationary phase.
View Article and Find Full Text PDFNature
January 2025
Department of Chemistry, The Scripps Research Institute, La Jolla, CA, USA.
C-H activation is the most direct way of functionalizing organic molecules. Many advances in this field still require specific directing groups to achieve the necessary activity and selectivity. Developing C-H activation reactions directed by native functional groups is essential for their broad application in synthesis.
View Article and Find Full Text PDFPolymers (Basel)
December 2024
School of Engineering, RMIT University, Melbourne, VIC 3000, Australia.
Entropy-Driven Ring-Opening Polymerisation represents an attractive mechanism to produce high-performance polymeric materials as it can be performed using neat, low-viscosity precursors and without the production of by-products or release of volatiles. Macrocyclic oligomers (MCOs) of polyether ketone ketone (PEKK) were synthesised and investigated as an method of forming this high-performance thermoplastic. Cyclic oligomers were successfully synthesised by pseudo-high dilution methods, and the reaction conditions were optimised through careful addition of starting materials and carbonate base selection.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!