Reactions of sulfenyl chlorides and their derivatives. 25. Reaction of chloride ion with thiiranium ions prepared by two different methods

Sçhmid, George H.; Strukelj, Mark; Dalipi, Snezana; Ryan, M. Dominic

doi:10.1021/jo00388a013

Cited by 18 publications

(5 citation statements)

References 2 publications

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“…This rearrangement clearly takes place during the reaction of the hydroxyl group with thionyl chloride, via a proposed mechanism shown in Scheme 2, which includes episulfonium salt (2A) as a possible intermediate. After the formation of the episulfonium salt, the chloride will attack the least sterically hindered carbon, 22 thus selectively opening the ring to form 2 and 7. As this reaction is very fast 2 and 7 are the kinetically most favourable products.…”

Section: Synthesismentioning

confidence: 99%

Synthesis, characterisation and crystal structures of new nickel complexes in S4 coordination spheres; an unprecedented rearrangement during ligand synthesis

Verhagen

Ellis

Lutz

et al. 2002

J. Chem. Soc., Dalton Trans.

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Two new nickel() complexes were synthesized with an S 4 coordination environment. These complexes were synthesized by in situ deprotection of thiouronium salts in the presence of nickel(). The ligands used are 4-mercapto-3,3-methyl-1-phenyl-2-thiabutane (Hbsms) and α,αЈ-bis(4-mercapto-3,3-methyl-2-thiabutyl)-o-xylene (H 2 xbsms). The former is a didentate ligand containing one thioether and one thiolate group and the latter is a dithioether dithiolate tetradentate ligand. The differences between these ligands upon coordination to nickel have been investigated. During the synthesis of these ligands, an unprecedented spontaneous rearrangement occurs, which is very fast and selective to a single product. The complexes were characterized by analytical, spectroscopic and electrochemical methods. The geometry of the nickel complexes is square planar according to the single-crystal X-ray structures. In [Ni(bsms) 2 ] the two ligands are coordinated with the thiolates in trans positions towards each other; in [Ni(xbsms)] the thiolates are in enforced cis positions. [Ni(bsms) 2 ] crystallizes in the triclinic space group P1 and has one centrosymmetric molecule in the unit cell. [Ni(xbsms)] crystallizes in the monoclinic space group P2 1 /c with two independent molecules in the asymmetric unit, however, the differences between these two molecules are very small. The Ni-S distances are 2.1730(4)-2.1909(6) Å and in the common range for thiolates and chelating thioethers.

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Section: Synthesismentioning

confidence: 99%

Synthesis, characterisation and crystal structures of new nickel complexes in S4 coordination spheres; an unprecedented rearrangement during ligand synthesis

Verhagen

Ellis

Lutz

et al. 2002

J. Chem. Soc., Dalton Trans.

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“…[25] These chlorosulfides tend to be rather unstable and are generally not isolated or separated. However, an alternative approach is to react an alkene with an electrophilic source of sulfur.…”

Section: Nucleophilic Attack On Thiiranium Ions Derived From Alkenesmentioning

confidence: 99%

Mechanisms of Sulfanyl (RS) Migrations: Synthesis of Heterocycles

Fox

House

Warren

2002

Angew. Chem. Int. Ed.

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Thiiranium (episulfonium) ions had been acknowledged as reaction intermediates for many years, but it was not until 1977 that Nicolaou demonstrated systematically that these reactive heterocyclic cations could be trapped by carboxylic acids to give lactones. In the years that followed this report, extensive research greatly extended the scope of this reaction, particularly with regard to the methods for generating thiiranium ions, the types of nucleophiles that are compatible with this reaction, and the selectivity involved in the cyclization reactions. For many years we have been using thiiranium ions for the synthesis of saturated heterocycles. Whereas Nicolaou's method relied on electrophilic sulfenylation of alkenes, we have generated thiiranium ions by displacement of a leaving group with neighboring-group participation by a sulfanyl group. Many of the examples we have reported are of cyclizations that are reversible and so where two (and in some cases more) products can result, the outcome of the reactions provides fundamental information about the relative stability of different heterocyclic ring systems. This Review will begin with a brief introduction to sulfanyl participation as a method for generating thiiranium (and thiolanium) ions, and will go on to explore the idea of using sulfanyl migrations in synthesis. Initially, emphasis will be placed on mechanisms of [1,2] sulfanyl migrations: we will look specifically at [1,2] sulfanyl migrations (usually PhS) with elimination, substitution, and cyclization. Emphasis will then shift to the factors that affect the outcome of cyclization reactions. In particular, we will cover cyclizations with hydroxy nucleophiles and examine situations in which there are more than one hydroxy nucleophile present. We will also examine cyclizations with other nucleophiles, namely amines and sulfides. After our discussion of [1,2] sulfanyl migrations, we will look very briefly at the scope of [1,4] sulfanyl participation, before finally drawing up some guidelines that (we hope) will help other organic chemists take advantage of the rearrangement reactions that the sulfanyl group has to offer.

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“…Die üblichsten Schwefel‐Elektrophile, die für diesen Zweck verwendet werden, sind Sulfenylchloride (RSCl). Das zuerst gebildete Thiiraniumion wird in Abwesenheit von Nucleophilen vom Chlorid‐Gegenion angegriffen, und es entstehen regioisomere Mischungen aus β ‐Chlorsulfiden 25. Diese Chlorsulfide sind gewöhnlich recht instabil und können meist nicht isoliert oder getrennt werden.…”

Section: Mechanismen Der Sulfanylwanderungenunclassified

Mechanismen der Sulfanylwanderung: die Synthese von Heterocyclen

2002

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Thiiraniumionen (Episulfoniumionen) sind seit vielen Jahren als Reaktionszwischenstufen bekannt, doch erst im Jahre 1977 zeigte Nicolaou im Rahmen einer systematischen Studie, dass diese reaktiven, heterocyclischen Kationen mit Carbonsäuren unter Bildung von Lactonen abgefangen werden können. In den folgenden Jahren wurde der Anwendungsbereich dieser Reaktion durch diverse Untersuchungen stark erweitert, insbesondere hinsichtlich der Methoden zur Generierung von Thiiraniumionen, der Kenntnisse über die mit der Reaktion verträglichen Nucleophiltypen und der Selektivität der Cyclisierung. Wir haben Thiiraniumionen seit vielen Jahren zur Synthese gesättigter Heterocyclen genutzt. Dabei werden die Thiiraniumionen durch Verdrängung einer Abgangsgruppe durch eine Sulfanylgruppe unter Nachbargruppenbeteiligung erzeugt, wohingegen Nicolaous Methode auf der elektrophilen Sulfenylierung von Alkenen beruht. Bei vielen der von uns beschriebenen Beispiele handelt es sich um reversible Cyclisierungen, und wenn zwei (und in einigen Fällen mehr) Produkte entstehen können, liefert der Ausgang der Reaktion grundlegende Informationen über die relative Stabilität der verschiedenen heterocyclischen Ringsysteme. Beginnend mit einer kurzen Einleitung über die Sulfanylgruppenbeteiligung als eine Methode zur Erzeugung von Thiiraniumionen (und Thiolaniumionen) wird in diesem Aufsatz im weiteren Verlauf die Idee beschrieben, Sulfanylwanderungen für die Synthese zu nutzen. Zuerst werden die Mechanismen von [1,2]‐Sulfanylwanderungen im Vordergrund stehen: Wir werden uns insbesondere mit [1,2]‐Sulfanylwanderungen (im Normalfall PhS) beschäftigen, bei denen eine Eliminierung, Substitution und Cyclisierung eintritt. Der Schwerpunkt verschiebt sich dann auf die Faktoren, die den Ausgang von Cyclisierungen beeinflussen. Hier werden vor allem Cyclisierungen in Gegenwart von Hydroxy‐Nucleophilen behandelt und Reaktionen untersucht, in denen mehr als ein Hydroxy‐Nucleophil zugegen ist. Cyclisierungen mit anderen Nucleophilen – Aminen und Sulfiden – werden ebenfalls angesprochen. Im Anschluss an die Diskussion über [1,2]‐Sulfanylwanderungen werden wir uns kurz mit dem Anwendungsbereich der [1,4]‐Sulfanylbeteiligung beschäftigen, um abschließend einige Richtlinien zu formulieren, die (so hoffen wir) anderen Chemikern der Organischen Chemie helfen werden, die Vorteile der Umlagerungen, die die Sulfanylgruppe eingehen kann, auszuschöpfen.

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Reactions of sulfenyl chlorides and their derivatives. 25. Reaction of chloride ion with thiiranium ions prepared by two different methods

Abstract: It has been found that the kinetically controlled product of the reaction of chloride ion with the thiiranium ion formed in the same solvent and at the same temperature by means of two different reactions is the one formed by attack at the least substituted carbon.

Cited by 18 publications

References 2 publications

Synthesis, characterisation and crystal structures of new nickel complexes in S4 coordination spheres; an unprecedented rearrangement during ligand synthesis

Synthesis, characterisation and crystal structures of new nickel complexes in S4 coordination spheres; an unprecedented rearrangement during ligand synthesis

Mechanisms of Sulfanyl (RS) Migrations: Synthesis of Heterocycles

Mechanismen der Sulfanylwanderung: die Synthese von Heterocyclen

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