This review is the first to collate and summarize main data on named and unnamed rearrangement reactions of peroxides. It should be noted, that in the chemistry of peroxides two types of processes are considered under the term rearrangements. These are conventional rearrangements occurring with the retention of the molecular weight and transformations of one of the peroxide moieties after O-O-bond cleavage. Detailed information about the Baeyer-Villiger, Criegee, Hock, Kornblum-DeLaMare, Dakin, Elbs, Schenck, Smith, Wieland, and Story reactions is given. Unnamed rearrangements of organic peroxides and related processes are also analyzed. The rearrangements and related processes of important natural and synthetic peroxides are discussed separately.
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http://dx.doi.org/10.3762/bjoc.12.162 | DOI Listing |
J Org Chem
January 2025
Applied Chemistry and Chemical Engineering, Graduate School of Engineering, Kogakuin University, Nakano 2665-1, Hachioji, Tokyo 192-0015, Japan.
The cascade aza-Prins/Friedel-Crafts reaction of homocinnamyloxycarbamate with electron-rich aromatic aldehydes has been successfully established. Most of the aromatic aldehydes react with the carbamate stereoselectively to generate -hydroindeno-1,2-oxazinanes. However, the cascade reactions of benzaldehydes bearing two methoxy groups at the -positions exhibit a unique stereochemical profile.
View Article and Find Full Text PDFChem Asian J
January 2025
Department of Chemistry, University at Albany, State University of New York, Albany, NY, 12222, USA.
The two-fold reduction of tetrabenzo[a,c,e,g]cyclooctatetraene (TBCOT, or tetraphenylene, 1) with K, Rb, and Cs metals reveals a distinctive core transformation pathway: a newly formed C-C bond converts the central eight-membered ring into a twisted core with two fused five-membered rings. This C-C bond of 1.589(3)-1.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
School of Chemistry, Dalian University of Technology, Dalian, 116024, P. R. China.
The Pd-catalyzed asymmetric hydrogenolysis rearrangement of allylic acetates using (s-Bu)BHK has been described, achieving the synthesis of axially chiral alkylidene cycloalkanes with excellent enantioselectivities (up to 99 % ee) and a wide substrate scope (30 examples of cyclohexanes and cyclobutanes). To the best of our knowledge, this is the first time to achieve synthesis of axially chiral olefins via asymmetric hydrogenolysis of allylic acetates. This methodology not only offers a novel synthetic pathway for non-atropisomeric axially chiral structures but also highlights the potential of asymmetric hydrogenolysis as a powerful tool in synthetic organic chemistry.
View Article and Find Full Text PDFNanoscale
January 2025
Institut de Chimie Moléculaire de l'Université de Bourgogne (ICMUB), UMR CNRS 6302, Université de Bourgogne, 9 avenue Alain Savary, 21078 Dijon, France.
Interfacing metal frameworks with carbon-based materials is attractive for the bottom-up construction of nanocomposite functional materials. The stepwise layering of difunctionalized diamantanes and gold metal from physical and chemical vapor deposition for the preparation of nanocomposites inverts the conventional preparation of metal-organic frameworks (MOFs) and self-assemblies, where the metal is introduced first, and this method delivers metal surfaces with modified properties originating from the sp-carbon core. However, appropriate diamondoid candidates for such an approach are rare.
View Article and Find Full Text PDFChem Sci
December 2024
Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China Hefei Anhui 230026 China
The packing of organic molecular crystals is often dominated by weak non-covalent interactions, making their rearrangement under external stimuli challenging to understand. We investigate a pressure-induced single-crystal-to-single-crystal (SCSC) transformation between two polymorphs of 2,4,5-triiodo-1-imidazole using machine learning potentials. This process involves the rearrangement of halogen and hydrogen bonds combined with proton transfer within a complex solid-state system.
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