Carbene transfer reactions are very important transformations in organic synthesis, allowing the generation of structurally challenging products by catalysed cyclopropanation, cyclopropenation, carbene C-H, N-H, O-H, S-H, and Si-H insertion, and olefination of carbonyl compounds. In particular, chiral and achiral metalloporphyrins have been successfully explored as biomimetic catalysts for these carbene transfer reactions under both homogeneous and heterogeneous conditions. In this work the use of synthetic metalloporphyrins (MPorph, M = Fe, Ru, Os, Co, Rh, Ir, Sn) as homogeneous or heterogeneous catalysts for carbene transfer reactions in the last years is reviewed, almost exclusively focused on the literature since the year 2010, except when reference to older publications was deemed to be crucial.
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http://dx.doi.org/10.3390/molecules23040792 | DOI Listing |
Chemistry
January 2025
Indian Institute of Technology Madras, Department of Chemistry, Chennai, Chennai, INDIA.
A series of significantly bulky mono- and di-substituted cyclic alkyl-amino carbene (cAAC)- functionalized cyclopentadiene ring (Cp) compounds were synthesized. The functionalization of the Cp ring with cAAC ligands makes them significantly bulkier, while retaining their ligation properties. These compounds display interesting fluorescence properties.
View Article and Find Full Text PDFAcc Chem Res
January 2025
Department of Chemistry and Research Center for Chemical Biology and Omics Analysis, College of Science, Southern University of Science and Technology, Shenzhen 518055, China.
ConspectusThe advancement of synthetic methodologies is fundamentally driven by a deeper understanding of the structure-reactivity relationships of reactive key intermediates. Carbyne anions are compounds featuring a monovalent anionic carbon possessing four nonbonding valence electrons, which were historically confined to theoretical constructs or observed solely within the environment of gas-phase studies. These species possess potential for applications across diverse domains of synthetic chemistry and ancillary fields.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
The remarkable efficiency with which enzymes catalyze small-molecule reactions has driven their widespread application in organic chemistry. Here, we employ automated fast-flow solid-phase synthesis to access catalytically active full-length enzymes without restrictions on the number and structure of noncanonical amino acids incorporated. We demonstrate the total syntheses of iron-dependent myoglobin (BsMb) and sperm whale myoglobin (SwMb).
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
City University of Hong Kong, Materials Sciences and Engineering, 83 Tat Chee Road, Kowloon, 999077, Kowloon Tong, HONG KONG.
Ir(III) complexes are particularly noted for their excellent photophysical properties in giving blue OLED phosphors. In this study, two distinctive carbene pro-chelates LAH2+ and LBH2+ (or LCH2+) were employed in preparation of heteroleptic Ir(III) complexes, to which LAH2+ bears a cyano substituted benzoimidazolium along with N-mesityl appendage, while LBH2+ (or LCH2+) carries the symmetrical benzoimidazolium entity. Notably, the reversible equilibration at high temperature was observed for m, f-ct14 and m, f-ct15 with a single LA chelate.
View Article and Find Full Text PDFAcc Chem Res
January 2025
Department of Chemistry, University of Wisconsin, 1101 University Avenue, Madison, Wisconsin 53706, United States.
ConspectusThe manipulation of strained rings is a powerful strategy for accessing the valuable chemical frameworks present in natural products and active pharmaceutical ingredients. Aziridines, the smallest N-containing heterocycles, have long served as building blocks for constructing more complex amine-containing scaffolds. Traditionally, the reactivity of typical aziridines has been focused on ring-opening by nucleophiles or the formation of 1,3-dipoles.
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