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Here we present a new method for synthesizing amide hemiaminal esters through the direct -methyl C-H esterification of -tosyl hydroxamates. This approach demonstrates good tolerance for a variety of functional groups and operates under mild, transition-metal-free conditions, thus providing an accessible and effective pathway to hemiaminal esters.
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http://dx.doi.org/10.1039/d5cc02570b | DOI Listing |
Chem Commun (Camb)
July 2025
Department of Pharmaceutical Sciences and Engineering, School of Food and Biological Engineering, Anhui Provincial International Science and Technology Cooperation Base for Major Metabolic Diseases and Nutritional Interventions, Hefei University of Technology, Hefei 230601, China.
Here we present a new method for synthesizing amide hemiaminal esters through the direct -methyl C-H esterification of -tosyl hydroxamates. This approach demonstrates good tolerance for a variety of functional groups and operates under mild, transition-metal-free conditions, thus providing an accessible and effective pathway to hemiaminal esters.
View Article and Find Full Text PDFOrg Biomol Chem
February 2025
Division of Pharmaceutical Sciences, Graduate School of Medical Sciences, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.
Azide-alkyne cycloaddition of cyclooct-2-yn-1-ol and 2-(azidophenyl)boronic acid proceeded rapidly at room temperature with complete regioselectivity to afford a triazole having a boronate ester group. The secondary interaction to form a boronate ion contributed to cycloaddition rate acceleration and the control of regioselectivity. The interaction to form an imine or hemiaminal was also evaluated.
View Article and Find Full Text PDFNat Commun
January 2024
National Institute of Biological Sciences, 7 Science Park Road, Zhongguancun Life Science Park, Beijing, 102206, China.
J Org Chem
February 2024
School of Pharmacy, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, China.
Enzyme-catalyzed dynamic kinetic resolution was applied to the one-pot regio- and enantioselective synthesis of 2,5-disubstituted tetrazole hemiaminal esters, among which 72% of the products were obtained in excellent enantiopurities (99% s). Tunable stereoselectivity was achieved by using different types of enzymes during the synthesis of a key intermediate for a clinic drug candidate. Successful preparation of tetrazole ester prodrugs and high catalyst recyclability further demonstrated the potential practical application of this protocol.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2024
Department of Chemistry, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford, OX1 3TA, UK.
Herein we report the first enantioselective total synthesis of (+)-incargranine A, in nine steps. The total synthesis was enabled by an enantioselective intramolecular organocatalysed desymmetrising Michael addition of a malonamate ester to a linked dienone substrate that established pivotal stereocentres with excellent enantio- and complete diastereoselectivity. Furthermore, a key hemiaminal intermediate was accessed by developing an iridium-catalysed reductive cyclisation, and the scope of this transformation was explored to produce a range of bicyclic hemiaminal motifs.
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