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2-Alkyl-substituted butadienes are synthesized starting from a masked butadiene reagent, which allows the regiospecific synthesis of 2-alkylbutadienes by lithiation and subsequent reaction with alkyl halides or aliphatic aldehydes. The regioselectivity of the reaction with allylic halides and aliphatic and aromatic aldehydes is studied.
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http://dx.doi.org/10.1021/jo9818881 | DOI Listing |
Org Biomol Chem
September 2025
Division of Chemistry and Chemical Engineering, University of Huddersfield, Queensgate, Huddersfield, HD1 3DH, UK.
In an attempt to react aminocyclopropenones with cyclic imines in order to synthesise amido-substituted pyrrolizidine natural products, we found that aminocyclopropenones undergo a previously unreported stereospecific and regiospecific catalyst-free, thermal ring-opening reaction with alcohols to yield β-enamino esters (also known as vinylogous carbamates or aminoacrylates). We report 21 examples in 45 to 97% isolated yield. The reaction occurs nucleophilic attack at the cyclopropenone carbonyl followed by regiospecific ring opening of the cyclopropenone with retention of alkene geometry.
View Article and Find Full Text PDFChem Commun (Camb)
September 2025
Department of Organic Synthesis and Process Chemistry, CSIR-Indian Institute of Chemical Technology, Hyderabad 500007, India.
A CFOH-catalysed tandem cyclization of -alkynylnaphthols and -quinone monoketals is disclosed. The CFOH catalyst activates alkynylnaphthol to generate an all-carbon tetrasubstituted VQM by nucleophilic addition to quinone monoketal (Michael addition). Furthermore, the CFOH catalyst triggers -quinone monoketal to generate an electrophilic oxocarbenium cation to be captured by -alkynylnaphthol regiospecifically, resulting in the formation of an all-carbon tetrasubstituted VQM, followed by an intramolecular cyclization to afford a series of 1-(3-arylbenzofuran-2-yl)naphthalen-2-ols.
View Article and Find Full Text PDFOrg Biomol Chem
August 2025
Technical Institute of Fluorochemistry (TIF), Institute of Advanced Synthesis (IAS), School of Chemistry and Molecular Engineering, State Key Laboratory of Material-Oriented Chemical Engineering, Nanjing Tech University, 30 South Puzhu Road, Nanjing 211816, P. R. China.
The dehydroxyfluorination of allylic alcohols stands as one of the most direct and effective methods for synthesizing versatile allylic fluorides. However, regioselectivity control in this transformation remains challenging. Herein, we demonstrate a fluorine effect-induced regiospecific dehydroxyfluorination of 3,3-difluoroallyl alcohols using Olah's reagent under mild reaction conditions.
View Article and Find Full Text PDFInt J Biol Macromol
September 2025
Department of Drug Science and Technology, University of Turin, Turin, Italy. Electronic address:
The high-fat content of hazelnuts, mainly triglycerides, makes them prone to lipid oxidation during storage, which has a big impact on their sensory and nutritional quality. The chemical pathways leading to hazelnut oxidative rancidity have been well characterized and are faster on free fatty acids. Lipase(s) enzymes are required in oilseeds to hydrolyse the ester bonds to free the single molecule of fatty acids.
View Article and Find Full Text PDFNat Commun
July 2025
State Key Laboratory of Chemical Biology, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China.
Chiral N-heterocycles such as piperidines and tetrahydroisoquinolines are privileged structural motifs in drug discovery and pharmaceutical industry. The development of efficient and practical asymmetric synthetic methods towards pharmaceutically important chiral N-heterocycles constitutes an important subject in synthetic chemistry. Asymmetric synthesis of 2,3-cis-disubstituted piperidines bearing two consecutive chiral centers is particularly challenging in terms of both diastereoselective and enantioselective control.
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