A variety of substituted benzisoxazoles has been prepared by the [3 + 2] cycloaddition of nitrile oxides and arynes. Both components, being highly reactive intermediates, have been generated in situ by fluoride anion from readily prepared aryne precursors and chlorooximes. The reaction scope is quite general, affording a novel, direct route to functionalized benzisoxazoles under mild reaction conditions.
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http://dx.doi.org/10.1021/ol902921s | DOI Listing |
J Biol Inorg Chem
January 2025
Department of Chemistry, Texas A&M University, College Station, TX, 77843, USA.
Related to the inactive form of nitrile hydratase, NHase, that contains Fe(NO) within tripeptide NS binding environment, the NO transfer reactivity of (bis-mercaptoethane diazacycloheptane)Fe(NO) and (bis-mercaptoethane diazadimethylethane)Fe(NO) is compared to Co(NO) analogs. Acceptors of NO include cobalt octaethylporphyrin and the [(NS)M] dimeric precursors in the synthesis of the Fe(NO) and Co(NO) biomimetics. Qualitative rates are augmented by a definitive kinetic study finding that rates of NO transfer from (NS)M(NO) to [(NS)M'] are dependent on M and M' as well as the hydrocarbon N to N and N to S linkers.
View Article and Find Full Text PDFJ Org Chem
January 2025
Laboratory of Pharmaceutical Chemistry, Kyoto Pharmaceutical University, Yamashina-ku, Kyoto 607-8412, Japan.
A one-pot, telescoped transformation of silyl ethers into cyanides that proceeds via silyl-ether oxidation mediated by nitroxyl-radical catalyst and [bis(trifluoroacetoxy)iodo]benzene followed by an imine formation-oxidation sequence using iodine and aqueous ammonia is reported. This transformation is effective for the site-selective transformation of benzylic and allylic silyl ethers in the presence of other silyl ethers. Using an -protected oxime and a catalytic amount of triflic acid instead of iodine/aqueous ammonia is also effective for cyanation.
View Article and Find Full Text PDFOrg Lett
January 2025
Department of Chemistry, Indian Institute of Technology Ropar, Rupnagar, Punjab 140001, India.
Herein, we report an electricity-driven activation of aziridine via direct anodic oxidation to give -heterocycles and 1,2-bifunctionalized products by excluding any oxidant/reductant or metal catalyst. Many structurally modified aziridines were employed in the presence of different nitriles. A large variety of nucleophiles were screened to furnish chemoselectively O-alkylated and C-alkylated products.
View Article and Find Full Text PDFChemphyschem
January 2025
Department of Chemistry, Durgapur Government College, West Bengal, Durgapur, 713214, India.
The relative reactivity and cis/trans selectivity of the intramolecular [3+2] cycloaddition (IM32CA) reactions of nitrile oxide (NO), azide (AZ), nitrile sulfide (NS) and nitrile ylide (NY), leading to functionalized heterocycles are studied within the Molecular Electron Density Theory. The kinetically controlled IM32CA reactions are predicted to be cis stereospecific, while the reaction feasibility follows the order NY>NS>NO>AZ with the respective activation Gibbs free energies of 13.7, 17.
View Article and Find Full Text PDFAcc Chem Res
January 2025
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, and Discipline of Intelligent Instrument and Equipment, Xiamen University, Xiamen 361005, P. R. China.
ConspectusMolecular photoelectrocatalysis, which combines the merits of photocatalysis and organic electrosynthesis, including their green attributes and capacity to offer novel reactivity and selectivity, represents an emerging field in organic chemistry that addresses the growing demands for environmental sustainability and synthetic efficiency. This synergistic approach permits access to a wider range of redox potentials, facilitates redox transformations under gentler electrode potentials, and decreases the use of external harsh redox reagents. Despite these potential advantages, this area did not receive significant attention until 2019, when we and others reported the first examples of modern molecular photoelectrocatalysis.
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