α-Oxo ketene dithioacetals and related compounds: versatile three-carbon synthons
About: This article is published in Tetrahedron.The article was published on 1986-01-01. It has received 299 citations till now. The article focuses on the topics: Ketene & Pericyclic reaction.
Citations
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TL;DR: This review aims to provide an intrinsic link between ketene dithioacetal groups and a variety of other functional groups, which has brought out many new facts that will assist in future designs.
Abstract: Ketene dithioacetals are versatile intermediates in organic synthesis. Extensive research, since the last decade, has given rise to new prospects in their chemistry. The objective of this review is twofold: first, to highlight the new prospects in the chemistry of functionalized ketene dithioacetals, and second, to provide an intrinsic link between ketene dithioacetal groups and a variety of other functional groups, which has brought out many new facts that will assist in future designs.
192 citations
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TL;DR: A mechanistic pathway for the Skraup quinoline synthesis is proposed that involves a fragmentation-recombination mechanism and the aniline component condenses with the alpha,beta-unsaturated ketone initially in a conjugate fashion, followed by a fragmentation to the corresponding imine and the ketone itself.
Abstract: The mechanism of the formation of substituted quinolines from anilines and α,β-unsaturated ketones has been studied by the use of 13C-labeled ketones in cross-over experiments. In the reaction of doubly labeled 13C(2,4) mesityl oxide, a 100% scrambling of the label in the quinoline product was observed, whereas only a small (5−10%) amount of the starting mesityl oxide showed scrambling of the label. Similarly, the reaction of triply labeled pulegone clearly shows that the label in the product is 100% scrambled, whereas the label in the starting pulegone is retained. On the basis of these studies, a mechanistic pathway for the Skraup quinoline synthesis is proposed that involves a fragmentation−recombination mechanism. The aniline component condenses with the α,β-unsaturated ketone initially in a conjugate fashion, followed by a fragmentation to the corresponding imine and the ketone itself. These fragments recombine to form the quinoline product.
173 citations
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TL;DR: A novel [5 + 1] annulation strategy is developed for the synthesis of highly substituted phenols and cyclohexenones from alpha-alkenoyl ketenedithioacetals and nitroalkanes.
Abstract: A novel [5 + 1] annulation strategy is developed for the synthesis of highly substituted phenols and cyclohexenones from α-alkenoyl ketenedithioacetals and nitroalkanes.
154 citations
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TL;DR: This review provides comprehensive knowledge on the chemistry of ketene N,S-acetals, which make them versatile and easy to use, especially in cyclization and multicomponent reactions for the synthesis of various heterocyclic systems and related natural products.
Abstract: Push–pull alkenes, which bear electron-donating and -accepting group(s) at both termini of a C═C double bond, respectively, are of interest not only for their unique electronic properties but also for their importance as versatile building blocks in organic synthesis. In the world of ketene acetals having the push–pull alkene skeleton, ketene N,S-acetal is most likely the biggest family according to the number and types of these compounds. The first ketene N,S-acetal compound was reported in 1956. As a cyclic ketene N,S-acetal compound, nithiazine, the first lead structure of neonicotinoid insecticides, was reported in 1978. The characteristics of ketene N,S-acetals, which have the structural feature of ketene S,S-acetals and enaminones, make them versatile and easy to use, especially in cyclization and multicomponent reactions for the synthesis of various heterocyclic systems and related natural products. There has been an increasing wealth of information about the synthesis and synthetic applications of...
115 citations
References
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01 Jan 1974TL;DR: The chemistry of the thiol group is studied in detail in order to establish a clear picture of the chiral stationary phase and its role in the polyene-like structure.
Abstract: The chemistry of the thiol group. , The chemistry of the thiol group. , کتابخانه دیجیتال جندی شاپور اهواز
601 citations
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TL;DR: In this paper, the herstellung von Dithiocarbonsauren aus CH-aciden Verbindungen und Schwefelkohlenstoff wird beschrieben.
Abstract: Die Herstellung von Dithiocarbonsauren aus CH-aciden Verbindungen und Schwefelkohlenstoff wird beschrieben. Die Alkylierung ihrer Salze fuhrt zu substituierten Ketenmercaptalen; bei der Oxydation entstehen Trithiacyclopentane und Dithiacyclobutane (Desaurine), letzter auch bei der Acylierung. Die Umsetzung mit Athylenimin liefert Thiazolidine. Die Struktur (Tautomerie) der Dithiocarbonsaureester und Ketenmercaptale wird an Hand der IR-Spektren diskutiert.
190 citations
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TL;DR: In this article, the Struktur des Benzoyl-dithioessaure-methylesters wird diskutiert und seine Umsetzung with Aminen beschrieben.
Abstract: Nitroketen-mercaptale (2, 4),-S.N-acetale (6) und -aminale (3) lassen sich aus Nitroalkanen herstellen. – Die Struktur des Benzoyl-dithioessigsaure-methylesters (9) wird diskutiert und seine Umsetzung mit Aminen beschrieben. – Aus Benzylcyanid, CS2/Alkali und Chloracet-amid entsteht 2-[Phenyl-cyan-methylen]-1.3-dithiolanon-(4) (18), das mit Aldehyden zu Cyaninfarbstoffen (20) reagiert. – Dithiocarbonsaureester vermogen sich an Chinone unter Bildung von 5-Hydroxy-benzo- und -naphtho-1.3-oxathiolen (23) zu addieren.
170 citations