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Keywords = diastereodivergence

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17 pages, 9983 KiB  
Article
Diastereodivergent Construction of Octahydrophenanthridinone and Octahydrophenanthridine Cores
by Chunzhao Sun, Hiromichi Nishikawa, Tsubasa Inokuma and Ken-ichi Yamada
Molecules 2025, 30(2), 371; https://doi.org/10.3390/molecules30020371 - 17 Jan 2025
Viewed by 854
Abstract
Diastereodivergent synthesis of octahydrophenanthridinone and octahydrophenanthridine skeletons, structural motifs often found in biologically active natural products, is described. We previously reported a total synthesis of a pancratistatin analog using novel octahydrophenanthridinone construction. In this study, we examined the generality of our method and [...] Read more.
Diastereodivergent synthesis of octahydrophenanthridinone and octahydrophenanthridine skeletons, structural motifs often found in biologically active natural products, is described. We previously reported a total synthesis of a pancratistatin analog using novel octahydrophenanthridinone construction. In this study, we examined the generality of our method and its extension to octahydrophenanthridine formation. Conjugate addition of diarylcuprates to nitrosocyclohexenes, which were generated in situ from 2-chlorocyclohexanone oximes, provided 2-arylcyclohexanone oximes. Subsequent reduction of the oxime moiety gave cis- and trans-configured amines. Both amines were separately converted into the corresponding octahydrophenanthridinones and octahydrophenanthridines via hexahydrophenanthridine intermediates. Full article
(This article belongs to the Special Issue Synthesis of Bioactive Compounds: Volume II)
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13 pages, 2367 KiB  
Article
Enantiodivergent Aldol Condensation in the Presence of Aziridine/Acid/Water Systems
by Adam Marek Pieczonka, Lena Marciniak, Michał Rachwalski and Stanisław Leśniak
Symmetry 2020, 12(6), 930; https://doi.org/10.3390/sym12060930 - 2 Jun 2020
Cited by 5 | Viewed by 3631
Abstract
A series of novel chiral imines was synthesized from corresponding aldehydes and 1-(2-aminoalkyl)aziridines with good chemical yields. Such imines were tested as catalysts in the direct asymmetric aldol reaction between aromatic aldehydes and acetone/cyclohexanone in the presence of catalytic amounts of water and [...] Read more.
A series of novel chiral imines was synthesized from corresponding aldehydes and 1-(2-aminoalkyl)aziridines with good chemical yields. Such imines were tested as catalysts in the direct asymmetric aldol reaction between aromatic aldehydes and acetone/cyclohexanone in the presence of catalytic amounts of water and an acidic additive. The corresponding aldol products were formed in excellent yields and with very high enantioselectivities (98% and 99% ee, respectively). Full article
(This article belongs to the Section Chemistry: Symmetry/Asymmetry)
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17 pages, 1174 KiB  
Article
Diastereodivergent and Enantioselective [4+2] Annulations of γ-Butenolides with Cyclic 1-Azadienes
by Chao Li, Kun Jiang and Ying-Chun Chen
Molecules 2015, 20(8), 13642-13658; https://doi.org/10.3390/molecules200813642 - 27 Jul 2015
Cited by 30 | Viewed by 6185
Abstract
An asymmetric annulation reaction of γ-butenolides and cyclic 1-azadienes containing a 1,2-benzoisothiazole-1,1-dioxide motif has been studied, proceeding in a tandem Michael addition-aza-Michael addition sequence. Endo-type cycloadducts bearing fused tetracyclic skeletons were isolated in fair yields and with high enantioselectivity (up to >99% [...] Read more.
An asymmetric annulation reaction of γ-butenolides and cyclic 1-azadienes containing a 1,2-benzoisothiazole-1,1-dioxide motif has been studied, proceeding in a tandem Michael addition-aza-Michael addition sequence. Endo-type cycloadducts bearing fused tetracyclic skeletons were isolated in fair yields and with high enantioselectivity (up to >99% ee) under the catalysis of modified cinchona alkaloid (DHQD)2PHAL. Besides, exo-type diastereomers could be produced using β-isocupreidine (β-ICD) as the catalyst, though with moderate enantioselectivity. Full article
(This article belongs to the Special Issue Brønsted Base Catalysis in Organic Synthesis)
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