Inter- and intramolecular additions of alkyl radicals, generated by SET photochemical decarboxylation reactions of free carboxylic acids, to electron-deficient alkenes take place under mild conditions as part of efficient routes for the formation of N-Boc gamma-amino acids and macrocyclic lactones.
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http://dx.doi.org/10.1021/ol9019277 | DOI Listing |
Acc Chem Res
January 2025
Department of Chemistry and Chemistry Institution for Functional Materials, Pusan National University, Busan 46241, Republic of Korea.
ConspectusControlling selectivity through manipulation of reaction intermediates remains one of the most enduring challenges in organic chemistry, providing novel solutions for selective C-C π-bond functionalization. This approach, guided by activation principles, provides an effective method for selective functional group installation, enabling direct synthesis of organic molecules that are inaccessible through conventional pathways. In particular, the selective functionalization of N-conjugated allenes and alkynes has emerged as a promising research focus, driven by advances in controlling reactive intermediates and activation strategies.
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January 2025
Condensed Matter Physics & Nanoscience Research Laboratory, Department of Physics and Material Science, Madan Mohan Malaviya University of Technology, Gorakhpur, 273010, U.P, India.
Nat Commun
January 2025
School of Chemistry, Chemical Engineering, and Biotechnology, Nanyang Technological University, Singapore, 637371, Singapore.
Acylation stands as a fundamental process in both biological pathways and synthetic chemical reactions, with acylated saccharides and their derivatives holding diverse applications ranging from bioactive agents to synthetic building blocks. A longstanding objective in organic synthesis has been the site-selective acylation of saccharides without extensive pre-protection of alcohol units. In this study, we demonstrate that by simply altering the chirality of N-heterocyclic carbene (NHC) organic catalysts, the site-selectivity of saccharide acylation reactions can be effectively modulated.
View Article and Find Full Text PDFACS Cent Sci
December 2024
Department of Molecular Sciences and Nanosystems, Ca' Foscari University of Venice, Via Torino 155, 30172 Mestre, Italy.
Computational generation of cyclic peptide inhibitors using machine learning models requires large size training data sets often difficult to generate experimentally. Here we demonstrated that sequential combination of Random Forest Regression with the pseudolikelihood maximization Direct Coupling Analysis method and Monte Carlo simulation can effectively enhance the design pipeline of cyclic peptide inhibitors of a tumor-associated protease even for small experimental data sets. Further studies showed that such -evolved cyclic peptides are more potent than the best peptide inhibitors previously developed to this target.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
University of Edinburgh, Chemistry, South Bridge, EH8 9YL, Edinburgh, UNITED KINGDOM OF GREAT BRITAIN AND NORTHERN IRELAND.
Organofluorine compounds are vital across multiple sectors, hence highly selective methods to install fluorine are of considerable importance. The deoxyfluorination of alcohols is a key approach to prepare organofluorine compounds, however, a highly secondary (2°)-selective deoxyfluorination of alcohols has not been realized to date. Herein, we report that borane-mediated deoxyfluorination results in high 2°-selectivity in inter- and intra-molecular competition reactions versus primary (1°), tertiary (3°) and even benzylic (Bn) alcohols.
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