We report the selective insertion of a range of borylene fragments into the E-E bonds (E = S, Se, Te) of cyclic boron dichalcogenides. This method provides facile synthetic access to a variety of symmetrical and unsymmetrical four- and five-membered rings.
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http://dx.doi.org/10.1039/c9sc00657e | DOI Listing |
Nat Commun
March 2025
The Institute for Advanced Studies, Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education, Wuhan University, 299 Bayi Road, 430072, Wuhan, Hubei, PR China.
Increasing attention has been paid to silacyclobutanes because of their wide application in ring opening and ring extension reactions. However, the synthesis of functionalized silacyclobutanes remains an unmet challenge because of the limited functional group tolerance of the reactions with organometallic reagents and chlorosilacyclobutanes. Herein, we report a conceptually different solution to this end through a visible-light-induced metal-free hydrosilylation of unactivated alkenes with hydrosilacyclobutanes.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
March 2025
Tokyo University of Science: Tokyo Rika Daigaku, Department of Applied Chemistry, 1-3 Kagurazaka, Shinjuku-ku, Tokyo, JAPAN.
Transition-metal-catalyzed asymmetric allylic substitution provides an efficient route to chiral organic molecules featuring an allyl moiety, key intermediates in the synthesis of biologically active compounds. However, the use of unsymmetrical 1,3-disubstituted allyl electrophiles has been severely constrained by the challenges of achieving both regio- and stereoselectivity simultaneously. Herein, we present γ-silyl-substituted allyl acetates as highly effective electrophiles for a regio- and enantioconvergent hydroallylation, enabling the construction of vicinal stereogenic centers.
View Article and Find Full Text PDFChemistry
March 2025
Department of Pharmaceutical Chemistry, University of Debrecen, 4032, Debrecen, Egyetem tér 1, Hungary.
α-Glycosyl thiols are key building blocks for the formation of stable thioglycoside mimetics of widespread and biologically relevant α-O-glycosides, which urges their efficient synthesis. Here, we demonstrate that the photoinitiated radical-mediated addition of thioacetic acid to 2-substituted glycals followed by selective S-deacetylation is a generally applicable and fully stereoselective method for the synthesis of 1,2-cis-α-glycosyl thiols. The low reactivity of thioacetic acid in the radical reaction was overcome by carrying out the reaction in AcOH at -80 °C, in frozen state, with UVA irradiation, achieving high yields irrespective of the sugar configurations.
View Article and Find Full Text PDFCarbohydr Res
February 2025
Medicinal and Process Chemistry Division, CSIR-Central Drug Research Institute, BS-10/1, Sector 10, Jankipuram Extension, Sitapur Road, P.O. Box 173, Lucknow, 226031, India; Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, 201002, India. Electronic address:
Herein, we demonstrate the application of unsymmetrical iodonium salts towards S-arylation of glycosyl thiols under metal-free conditions, affording a various stereoretentive thioarylglycosides in moderate to good yields. The application of an inorganic base CsCO enables the C-S bond formation under mild and experimentally simple conditions at room temperature. The proper choice of auxiliary of the unsymmetrical iodonium salt enables the access to diverse functionalized aryl moieties including biphenyl groups and its incorporation into thioarylglycosides.
View Article and Find Full Text PDFOrg Lett
March 2025
Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur 741246, India.
Phosphorus-embedded porous organic polymers (P-POPs) play a vital role in catalysis and sustainable chemical synthesis. This study uses an olefin-linked P-POP to stabilize Pd nanoparticles that catalyze Larock's annulation to synthesize symmetrical indenones in high yields. Unsymmetric indenones were obtained with exclusive regioselectivities by employing an intramolecular dicarbofunctionalization of a modular alkyne.
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