Lithium iodide enables regioconvergent C-F bond functionalization of isomeric Morita-Baylis-Hillman fluorides with carbon, sulfur, and nitrogen nucleophiles. The defluorinative carbon-carbon and carbon-heteroatom bond formations give multifunctional compounds in excellent yields and with good to high diastereoselectivities at room temperature. The possibility of catalytic enantioselective allylation is also discussed.
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Regioconvergent Nucleophilic Substitutions with Morita-Baylis-Hillman Fluorides.
J Org Chem
August 2024
Department of Chemistry, Georgetown University, 37th and O Streets, Washington, District of Columbia 20057, United States.
Lithium iodide enables regioconvergent C-F bond functionalization of isomeric Morita-Baylis-Hillman fluorides with carbon, sulfur, and nitrogen nucleophiles. The defluorinative carbon-carbon and carbon-heteroatom bond formations give multifunctional compounds in excellent yields and with good to high diastereoselectivities at room temperature. The possibility of catalytic enantioselective allylation is also discussed.
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Angew Chem Int Ed Engl
November 2023
Department of Chemistry, Wayne State University, Detroit, MI 48202, USA.
Although there are many methods for the asymmetric synthesis of monosubstituted allylic fluorides, construction of enantioenriched 1,2-disubstituted allylic fluorides has not been reported. To address this gap, we report an enantioselective synthesis of 1,2-disubstituted allylic fluorides using chiral diene-ligated rhodium catalyst, Et N ⋅ 3HF as a source of fluoride, and Morita Baylis Hillman (MBH) trichloroacetimidates. Kinetic studies show that one enantiomer of racemic MBH substrate reacts faster than the other.
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Department of Chemical Sciences, Ariel University, Ariel 4070000, Israel.
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J Org Chem
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Department of Life Science and Applied Chemistry, Department of Nanopharmaceutical Sciences, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-5888, Japan.
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View Article and Find Full Text PDFCopper-Catalyzed One-Pot Borylative Aldolisation β-Fluoride Elimination for the Formal Addition of Acrylates to Carbonyl Moieties.
Chemistry
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