An efficient method for the stereoselective synthesis of (Z)-alpha-arylacrylates is described. Treatment of alpha-hydroxyesters with triflic anhydride and pyridine at 0 degrees C followed by warming to room temperature afforded the corresponding (Z)-alpha-aryl-alpha,beta-unsaturated esters in very good yields and excellent stereoselectivity.
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http://dx.doi.org/10.1021/jo060586t | DOI Listing |
JACS Au
January 2025
Laboratoire de Synthèse Organique (LSO-UMR 7652) CNRS, Ecole Polytechnique, ENSTA-Paris, Institut Polytechnique de Paris 828 Bd des Maréchaux, 91128 Palaiseau Cedex, France.
We report here the first example of a copper-catalyzed transformation involving nitro allyl derivatives. This borylation reaction, which exploits the high versatility of the aforementioned precursor, tolerates a variety of functional groups and allows practical, scalable, and highly straightforward access to diversely substituted allylboronic esters in high yields. The method was also extended to allyl sulfones, which provides a very complementary approach, offering additional structural diversity along with improved stereoselectivities.
View Article and Find Full Text PDFChem Sci
January 2025
Department of Chemistry, University of York York YO10 5DD UK
C-N atropisomeric amides are important compounds in medicinal chemistry and agrochemistry. Atropselective methods for their synthesis are therefore important. In this study, a novel strategy to make C-N atropisomeric amides based on intramolecular acyl transfer a tethered Lewis basic pyridine or tertiary amine group is reported.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Organic and Inorganic Chemistry Department, Instituto Universitario de Química Organometálica "Enrique Moles", University of Oviedo. Avenida Julián Clavería 8, 33006 Oviedo, Asturias, Spain.
Several chemoenzymatic pathways have been developed for the stereoselective production of the drug tamsulosin. The interest in the exclusive synthesis of its ()-enantiomer lies in the greater activity compared to that displayed by its ()-counterpart for the treatment of kidney stones and benign prostatic hyperplasia disease. Using different types of biocatalysts such as lipases, alcohol dehydrogenases and transaminases, three complementary strategies have been studied to introduce chirality into a key synthetic precursor.
View Article and Find Full Text PDFOrg Lett
January 2025
Department of Chemistry, University of Tennessee, Knoxville, Knoxville, Tennessee 37996, United States.
Construction of vinylsilane building blocks is important for advancing the synthesis of complex small molecules and natural products. Herein, we report a highly regio- and stereoselective copper-catalyzed hydrosilylation of unsymmetrical internal aryl alkynes. The reaction is performed across a broad scope of internal aryl alkynes, providing exclusive access to α-vinylsilane alkenyl arene products, including several silylated small molecule drug analogs.
View Article and Find Full Text PDFAnal Chem
January 2025
Beijing National Laboratory for Molecular Sciences, CAS Research/Education Center for Excellence in Molecular Sciences, Key Laboratory of Analytical Chemistry for Living Biosystems, Beijing Mass Spectrum Center, Institute of Chemistry Chinese Academy of Sciences, Beijing 100190, China.
Monounsaturated fatty acids (MUFA) are an important class of nutrients and are involved in lipid metabolism. The positions of the C=C bond and cis-trans isomerism have a significant influence on their physiological activity. However, simultaneously detecting these two structural properties has been challenging due to multiple isomers of MUFA.
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