Chiral nitroalkenes are used for the first time in Michael additions of aldehydes, catalyzed by pyrrolidine derivatives. They yield the same major stereoisomer with either ()-proline or ()-proline, but this asymmetric induction does not overcome the effect of sterically more congested catalysts. Nitrocyclobutane intermediates are often formed, which are more stable than those from ()-1-nitro-2-phenylethene. The cyclobutanes and final products were characterized by 2D NMR and chemical correlations.
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http://dx.doi.org/10.1021/acs.orglett.0c03609 | DOI Listing |
Angew Chem Int Ed Engl
November 2024
Hefei National Research Center for Physical Sciences at the Microscale, Department of Chemistry, University of Science and Technology of China, Hefei, Anhui, 230026, P. R. China.
Org Biomol Chem
June 2024
Department of Chemistry, Sharif University of Technology, Tehran 11155-9516, Iran.
Bromonitroalkenes are useful molecules in synthetic organic chemistry. They are mainly prepared from nitroalkenes bromination reactions. In this review, the application of bromonitroalkenes as partners in the reaction with a diversity of mono- and bi-functional molecules, including aldehydes and ketones, active methylene compounds, 1,2-dicarbonyls, enamines, enols, electron-rich arenes, amidines, azomethine ylides, azirines, diazo compounds, and many others, is reviewed.
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September 2023
Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Prof. Sobouti Boulevard, PO-Box 45195-1159, Zanjan, 45137-66731, Iran.
Chiral chloro-indeno pybox has served as a new ligand for the Yb(OTf)-catalyzed asymmetric Friedel-Crafts alkylation reaction of indoles with nitroalkenes. The tunable nature of pybox ligands enables the rational design of catalysts for optimal performance in terms of both activity and stereoselectivity in a Friedel-Crafts-type reaction. Good to excellent yields and enantioselectivities were obtained for a relatively wide range of substrates, including sterically hindered compounds, under optimized reaction conditions.
View Article and Find Full Text PDFChemistry
September 2023
Department of Chemistry, Sungkyunkwan University, Suwon, 16419, Korea.
Chiral allylic amines are valuable building blocks for biologically important compounds and natural products. In this study, we present the use of cooperative cation-binding catalysis as an efficient method for synthesizing chiral allylic amines. By utilizing a chiral oligoEG and potassium fluoride as a cation-binding catalyst and base, respectively, a wide range of biologically relevant chiral 2-nitroallylic amines are obtained with excellent enantioselectivities (up to >99 % ee) through the organocatalytic asymmetric aza-Henry-like reaction of β-monosubstituted and β,β-disubstituted nitroalkenes with α-amidosulfones as imine precursors.
View Article and Find Full Text PDFMolecules
April 2023
Dipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, 20133 Milano, Italy.
Starting from commercially available ketones, a reproducible and reliable strategy for the synthesis of tetrasubstituted nitroalkenes was successfully developed, using a two-step procedure; the HWE olefination of the ketone to form the corresponding α,β-unsaturated esters is followed by a nitration reaction to introduce the nitro group in the α position of the ester group. The enantioselective organocatalytic reduction of these compounds has also been preliminarily studied, to access the functionalized enantioenriched nitroalkanes, which are useful starting materials for further synthetic elaborations. The absolute configuration of the reduction product was established by chemical correlation of the chiral nitroalkane with a known product; preliminary DFT calculations were also conducted to rationalize the stereochemical outcome of the organocatalytic enantioselective reduction.
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