A method for the synthesis of a wide range of fused thiophenes, including those fused with lactams, lactones, or cyclic ethers, was developed from a rhodium-catalyzed intramolecular transannulation reaction of alkynyl thiadiazoles. This transannulation reaction provides an efficient platform for the construction of a variety of 5,n-fused thiophenes from readily available starting materials together with the release of molecular nitrogen.
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http://dx.doi.org/10.1021/acs.joc.6b02614 | DOI Listing |
Inorg Chem
January 2025
Department of Chemistry, University of Richmond, Richmond, Virginia 23173, United States.
Copper(I) complexes of isobutyl- () and isopropyl-substituted () proazaphosphatranes have been synthesized. Structural and computational studies of a series of monomeric complexes CuX (X = Cl, Br, I) and dimeric [CuCl] provide insight into the transannulation within and steric properties of the proazaphosphatrane ligand. These halide complexes are competent precatalysts in a model borylation reaction, and the silylamido complex CuN(TMS) catalyzes hydrosilylation of benzaldehyde under mild conditions.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 160 00 Prague, Czechia.
Diazidodifluoromethane was prepared from dibromodifluoromethane, sodium azide and an alkanethiolate initiator. It represents the first example of a diazidomethane that is stable enough to be used in synthesis. The stability of (poly)azidomethanes was explored with calculations.
View Article and Find Full Text PDFBiochemistry
December 2024
Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, United States.
Sabinene is a plant natural product with a distinctive strained [3.1.0] bicyclic ring system that is used commercially as a spicy and pine-like fragrance with citrus undertones.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
June 2024
College of Chemistry and Chemical Engineering, Qingdao University, Ningxia Road 308#, Qingdao, 266071, China.
Nickel-catalyzed transannulation reactions triggered by the extrusion of small gaseous molecules have emerged as a powerful strategy for the efficient construction of heterocyclic compounds. However, their use in asymmetric synthesis remains challenging because of the difficulty in controlling stereo- and regioselectivity. Herein, we report the first nickel-catalyzed asymmetric synthesis of N-N atropisomers by the denitrogenative transannulation of benzotriazones with alkynes.
View Article and Find Full Text PDFJ Org Chem
December 2023
Instituto de Química Rosario, Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario-CONICET, Suipacha 531, Rosario S2002LRK, Argentina.
A versatile one-pot strategy for the generation of compounds of synthetic interest has been presented, promoting the development of practical processes. First, the transannulation of sulfonyltriazoles through alkenes and rhodium catalysis was described, giving 2,3-dihydropyrroles in 13-76% yield. As contributions of the strategy, the evaluation of alkenes with different properties, and the use of only drops of solvent (0.
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