Site-selective photoredox reactions with aromatic olefins enable direct alkylation of unprotected -inositol at C4. The efficacy of these reactions can be finely tuned by modifying the structures of HAT reagents. These reactions open the possibility of selective C-H alkylations of -inositol without the need for multi-step protection-deprotection strategies.
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http://dx.doi.org/10.1039/d2cc03569c | DOI Listing |
Nat Commun
January 2025
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN, 46556, USA.
Complementary methods toward the selective functionalization of indole and oxindole frameworks employing an alternative strategy in heteroaryl C-H functionalizations are presented herein. This work focuses on a catalyst-controlled, site selective C-H activation/functionalization of 3-acyl indoles, wherein an amide serves as a robust and versatile directing group capable of undergoing concomitant 1,2-acyl translocation/C-H functionalization in the presence of a Rh/Ag co-catalysts to provide the cross-coupled adducts in high yields. In contrast, the use of Ir/Ag catalysts subverted the 1,2-acyl migration to afford the corresponding C2-functionalized products in good to excellent yields.
View Article and Find Full Text PDFOrg Lett
December 2024
Department of Chemistry and Molecular Biology, University of Gothenburg, SE-41296 Gothenburg, Sweden.
We present a highly selective protocol for the benzylation of -aryl amides. This method offers mild conditions, excellent site specificity, and scalability, enabling the synthesis of diarylmethane amides and dibenzoazepines. The protocol allows for one-pot diagonal dibenzylation of dianilides, creating valuable precursors for pharmaceutically active compounds and addressing limitations in current direct C-H activation methodologies.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Faculty of Pharmaceutical Sciences, Hokkaido University, Kita-ku, Sapporo, Japan.
A site-selective functionalization of a C(sp)-H bond was achieved in the presence of an intrinsically more reactive C(sp)-H bond by controlling the orientation of a directing group via a photo-induced E/Z isomerization of an oxime ether. By combining E/Z isomerization and an electron deficient Cp*Ir(III) catalyst, the scope of oxime ethers in C(sp)-H functionalization was successfully expanded. Based on this strategy, the order of C-H activation was switchable and successive C(sp)-H/C(sp)-H and C(sp)-H/C(sp)-H double functionalizations were accomplished to construct densely functionalized structures.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Institute of Chemical Research of Catalonia (ICIQ-CERCA), The Barcelona Institute of Science and Technology, Països Catalans 16, 43007 Tarragona, Spain.
A novel platform for the skeletal editing of single C-C bonds via a single-carbon insertion has been developed using diazirines. This strategy involves the photogeneration of arylchlorocarbenes as carbynoid species that undergo site-selective carbene insertion into tertiary C-H bonds and a subsequent Wagner-Meerwein rearrangement promoted by a silver salt. Our skeletal editing strategy based on a formal selective carbyne C-C bond insertion has been demonstrated in six core-to-core conversions, including linear and cyclic benzylic substrates, alkanes and late-stage functionalizations.
View Article and Find Full Text PDFChem Sci
January 2025
Wöhler Research Institute for Sustainable Chemistry (WISCh), Georg-August-Universität Tammannstraße 2 37077 Göttingen Germany
The position-selective C-H bond activation of arenes has long been a challenging topic. Herein, we report an expedient ruthenium-electrocatalyzed site-selective -C-H phosphorylation of arenes driven by electrochemical hydrogen evolution reaction (HER), avoiding stoichiometric amounts of chemical redox-waste products. This strategy paved the way to achieve unprecedented ruthenaelectro-catalyzed -C-H phosphorylation with excellent levels of site-selectivity.
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