Halogenobis(N,N-dialkyldithiocarbamato)iron(III) complexes as potential catalysts for halogen addition reactions to alkenes

Tsipis, Constantinos A.; Katsoulos, G.A.; Vakoulis, F. D.

doi:10.1039/c39850001404

Cited by 7 publications

(4 citation statements)

References 2 publications

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“…Although Denmark, Cresswell and Eey have recently achieved the first catalytic, syn-stereospecific dichlorination of alkenes (see Section 4.4.2), [52] an enantioselective variant of this reaction, as well as an analogous syndibromination process,remain elusive. [67]…”

Section: Alkene Dihalogenationmentioning

confidence: 99%

“…However, the option of diastereodivergent dihalogenation from a single alkene geometry is clearly preferable and, at any rate, the ( E )‐isomers of cyclic alkenes are inaccessible for ring sizes below eight. Although Denmark, Cresswell and Eey have recently achieved the first catalytic, syn ‐stereospecific dichlorination of alkenes (see Section 4.4.2),52 an enantioselective variant of this reaction, as well as an analogous syn ‐dibromination process, remain elusive 67…”

Section: Challenges For Stereoselective Catalysismentioning

confidence: 99%

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Catalytic, Stereoselective Dihalogenation of Alkenes: Challenges and Opportunities

2015

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Although recent years have witnessed significant advances in the development of catalytic, enantioselective halofunctionalizations of alkenes, the related dihalogenation of olefins to afford enantioenriched vicinal dihalide products remains comparatively underdeveloped. However, the growing number of complex natural products bearing halogen atoms at stereogenic centers has underscored this critical gap in the synthetic chemist's arsenal. This Review highlights the selectivity challenges inherent in the design of enantioselective dihalogenation processes, and formulates a mechanism-based classification of alkene dihalogenations, including those that may circumvent the "classical" haliranium (or alkene-dihalogen π-complex) intermediates. A variety of metal and main group halide reagents that have been used for the dichlorination or dibromination of alkenes are discussed, and the proposed mechanisms of these transformations are critically evaluated. AbstractCatalysis of alkene dihalogenation , under different activation modes, with control over both the absolute and relative stereochemical course of dihalogen addition, is one of the most vexing problems in stereoselective synthesis. Dihalogenations that circumvent the "classical" haliranium (or alkene-dihalogen π complex) intermediates provide new and exciting opportunities for catalysis, potentially having broader implications for the design of stereoselective alkene difunctionalizations.

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Section: Alkene Dihalogenationmentioning

confidence: 99%

Section: Challenges For Stereoselective Catalysismentioning

confidence: 99%

Catalytic, Stereoselective Dihalogenation of Alkenes: Challenges and Opportunities

2015

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“…Zwar gelang Denmark et al. vor kurzem die erste katalytische syn ‐stereospezifische Dichlorierung von Alkenen (siehe Abschnitt 4.4.2),52 eine enantioselektive Variante dieser Reaktion wurde aber nicht erzielt, ebensowenig wie eine analoge syn ‐Dibromierung 67…”

Section: Herausforderungen Für Die Stereoselektive Katalyseunclassified

Katalytische stereoselektive Dihalogenierung von Alkenen: Herausforderungen und Chancen

2015

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Während in den letzten Jahren signifikante Fortschritte bei der Entwicklung katalytischer, enantioselektiver Halogenfunktionalisierungen von Alkenen erzielt wurden, ist die verwandte Dihalogenierung von Olefinen zur Bildung enantiomerenangereicherter vicinaler dihalogenierter Produkte vergleichsweise unterentwickelt. Allerdings verweist die steigende Anzahl komplexer Naturstoffe mit Halogenatomen an stereogenen Zentren deutlich auf diese Lücke im Arsenal der Synthesechemie. Dieser Aufsatz behandelt die Herausforderungen bei der gezielten Entwicklung enantioselektiver Dihalogenierungsprozesse und formuliert eine mechanismusbasierte Klassifizierung der Dihalogenierung von Alkenen, einschließlich solcher, welche die “klassischen” Haliranium‐Intermediate (oder Alkendihalogen‐π‐Komplexe) umgehen können. Die Anwendung zahlreicher Metall‐ und Hauptgruppenhalogenide als Reagentien zur Dichlorierung oder Dibromierung von Alkenen wird diskutiert, und die vorgeschlagenen Mechanismen dieser Transformationen werden kritisch beurteilt.

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“…In particular, the molecular halogen interacts weakly in an end-on fashion with the halide ligand of the mononuclear complexes, forming an extended tetratomic bridging unit, {X-X'-X'-X} 2-, between the two paramagnetic centres. Consequently, the binuclear complexes have been proved [7] to be potential carriers of activated molecular halogens and therefore very reactive in halogentransfer reactions.As an extension of our previous work [8][9][10] on thermal studies of metal diothiocarbamate complexes, a thermal investigation of the dihalide-bridged …”

mentioning

confidence: 99%

Thermal decomposition of some homobinuclear dihalide-bridged iron(III) complexes

Lalia‐Kantouri

Katsoulos

Vakoulis

1986

Journal of Thermal Analysis

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Thermal studies by TG and DTG on some homobinuclear dihalide-bridged iron(Ill) complexes of the general type [Fe(S2CNR2)2X]2~-X~) were carried out in air and nitrogen atmospheres. The apparent activation energies were determined by graphical methods and the TTN temperatures were calculated from the TG profiles. Finally, a possible mechanism of the decomposition is suggested on the basis of the pyrolysis and mass spectral data.In previous papers, results have been reported on the reactions of molecular halogens (X~) with the square-pyramidal complexes [Fe(S2CNR2)2X] (X = CI, Br, I) [1][2][3]. The salient feature of these reactions is the effect of the alkyl substituent in the dithiocarbamato ligand on the composition of the products obtained [4,5]. In this respect, a general mechanism accounting for the variety of products formed has been proposed [3].In this paper, we focus our attention on the binuclear iron(Ill) complexes formulated [2] as [Fe(S2CNR2)2X]2(/~-X~), where R = Me, Et, pri; X' = Br, I. M6ssbauer and magnetic measurements on this very interesting class of compounds, as well as an X-ray crystal structure determination [6] of another derivative of this series containing the pyrrolidinyldithiocarbamato ligand, have established the presence of the molecular halogen in the form of a bridging unit mediating the formation of weakly coupled dimers with antiferromagnetic interaction. In particular, the molecular halogen interacts weakly in an end-on fashion with the halide ligand of the mononuclear complexes, forming an extended tetratomic bridging unit, {X-X'-X'-X} 2-, between the two paramagnetic centres. Consequently, the binuclear complexes have been proved [7] to be potential carriers of activated molecular halogens and therefore very reactive in halogentransfer reactions.As an extension of our previous work [8][9][10] on thermal studies of metal diothiocarbamate complexes, a thermal investigation of the dihalide-bridged

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Halogenobis(N,N-dialkyldithiocarbamato)iron(III) complexes as potential catalysts for halogen addition reactions to alkenes

Abstract: In the presence of a catalytic amount of iron(iii) halogenobisdithiocarbamates, the addition of molecular halogens to alkenes occurs rapidly to afford cis-addition products.

Cited by 7 publications

References 2 publications

Catalytic, Stereoselective Dihalogenation of Alkenes: Challenges and Opportunities

Catalytic, Stereoselective Dihalogenation of Alkenes: Challenges and Opportunities

Katalytische stereoselektive Dihalogenierung von Alkenen: Herausforderungen und Chancen

Thermal decomposition of some homobinuclear dihalide-bridged iron(III) complexes

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