The selective functionalization of remote C-H bonds via intramolecular hydrogen atom transfer (HAT) is transformative for organic synthesis. This radical-mediated strategy provides access to novel reactivity that is complementary to closed-shell pathways. As modern methods for mild generation of radicals are continually developed, inherent selectivity paradigms of HAT mechanisms offer unparalleled opportunities for developing new strategies for C-H functionalization. This review outlines the history, recent advances, and mechanistic underpinnings of intramolecular HAT as a guide to addressing ongoing challenges in this arena.
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http://dx.doi.org/10.1055/s-0036-1591930 | DOI Listing |
J Vitreoretin Dis
December 2024
Retina Consultants of Texas, Houston, TX, USA.
To investigate how home optical coherence tomography (OCT) influences the clinical decision-making of retina specialists for the management of neovascular age-related macular degeneration (nAMD). In this retrospective imaging review, 15 retina specialists each evaluated 10 home OCT data segments from 29 eyes being treated for nAMD. Based on OCT data, indications were identified for when eyes should be treated, which antivascular endothelial growth factor should be used, and the specific retinal fluid and time thresholds for notification.
View Article and Find Full Text PDFOrg Lett
December 2024
Department of Chemistry, Indian Institute of Technology Bombay, Mumbai 400076, India.
Remote C4-H functionalization of -naphthoic acids is highly challenging due to the presence of proximally more accessible C-H bonds at the C2 and C8 positions. Herein, we report the first palladium-catalyzed direct C4 arylation of 1-naphthamides with high regioselectivity and excellent functional group compatibility. Diverse aryl couples were found to be compatible with C4 arylation.
View Article and Find Full Text PDFChem Sci
December 2024
School of Materials Science and Engineering, PCFM Lab, the Key Laboratory of Low-carbon Chemistry & Energy Conservation of Guangdong Province, Sun Yat-sen University Guangzhou 510006 P. R. China
Metal-ligand cooperation (MLC) is an essential strategy in transition metal catalysis. Traditional NH-based and OH-based MLC catalysts, as well as the later developed (de)aromatization strategy, have been widely applied in atom-economic borrowing hydrogen/hydrogen auto-transfer (BH/HA) reactions. However, these conventional MLC approaches are challenging for low-coordination and low-activity coinage metal complexes, arising from the instability during (de)protonation on the coordination atom, the constraint in linear coordination, and possible poisoning due to extra functional sites.
View Article and Find Full Text PDFOrg Lett
December 2024
Chemical Development, Pharmaceutical Technology & Development, Operations, AstraZeneca, Macclesfield, SK10 2NA, U.K.
Advancements in transition metal catalyzed C-H activation/functionalization cascades have allowed the synthetic chemist's toolbox to be significantly expanded. Despite this, protocols for the remote alkynylation of linear aliphatic amines still remain limited. Herein, a palladium-catalyzed directing-group approach to alkynylation of aliphatic amines is disclosed.
View Article and Find Full Text PDFJ Org Chem
December 2024
School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China.
By using weakly coordinating amines, we developed remote C-H alkynylation with precise control of reactivity and regioselectivity, enabling modification of complex drugs, natural products, and materials. The readily transformable alkyne-containing amine products would facilitate expedient delivery of molecular libraries of functionalized amines and medium -heterocycles, which are previously elusive to access. Moreover, the introduced alkyne functionality could serve as a versatile handle to expand the diversity and synthetic application of this remote C-H functionalization.
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