Photoredox cycling during UV irradiation of ferrocyanide ([FeII(CN)6]4-) in the presence of stoichiometric sulfite (SO32-) is shown to be an extremely effective way to drive the reductive homologation of hydrogen cyanide (HCN) to simple sugars and precursors of hydroxy acids and amino acids.
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http://dx.doi.org/10.1039/c8cc01499j | DOI Listing |
Nat Commun
November 2024
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh, India.
Skipped dienes are among the most prevalent motifs in a vast array of natural products, medicinal compounds, and fatty acids. Herein, we disclose a straightforward one-step reductive protocol under Co/PC for the synthesis of diverse 1,4-dienes with excellent regio- and stereoselectivity. The protocol employs allenyl or allyl carbonate as π-allyl source, allowing for the direct synthesis of skipped diene with a broad range of alkynes including terminal alkynes, propargylic alcohols, and internal alkynes.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Laboratory of Catalysis and Organic Synthesis, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, CH-1015, Lausanne, Switzerland.
We report herein our studies on the direct photoactivation of carbonyl cyclopropanes to give biradical intermediates, leading to selective cleavage of the more substituted carbon-carbon bond. Depending on the substrate structure, extended alkenes were isolated or directly reacted in a photo-Nazarov process to give bicyclic products. Based on these results, a unified reductive ring-opening reaction was developed by using diphenyl disulfide as a hydrogen atom transfer (HAT) reagent.
View Article and Find Full Text PDFJ Am Chem Soc
November 2024
Laboratory of Synthesis and Natural Products (LSPN), Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne (EPFL-SB-ISIC-LSPN), BCH5304, CH-1015 Lausanne, Switzerland.
Org Lett
October 2024
Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan.
We present the reductive homologation of nitroalkanes through the utilization of the denitrative aminoalkylation reaction. This transformation is accomplished by the radical-radical coupling of alkyl radicals derived from nitroalkanes and persistent aminoalkyl radicals. By capitalizing on the diverse α-functionalization of nitroalkanes, α,β-multifunctionalized amines can be readily accessed.
View Article and Find Full Text PDFChem Sci
June 2023
School of Chemical and Physical Sciences, Victoria University of Wellington P. O. Box 600 Wellington New Zealand
We report the reaction of the potassium aluminyl, K[Al(NON)] ([NON] = [O(SiMeNDipp)], Dipp = 2,6-iPrCH) with a series of isocyanide substrates (R-NC). In the case of Bu-NC, degradation of the isocyanide was observed generating an isomeric mixture of the corresponding aluminium cyanido-κ and -κ compounds, K[Al(NON)(H)(CN)]/K[Al(NON)(H)(NC)]. The reaction with 2,6-dimethylphenyl isocyanide (Dmp-NC), gave a C-homologation product, which in addition to C-C bond formation showed dearomatisation of one of the aromatic substituents.
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