Reactivity Pattern of Bis(propargyloxy) Disulfides: Tandem Rearrangements and Cyclizations

Braverman, S.; Pechenick-Azizi, Tatiana; Gottlieb, Hugo E.; Sprecher, Milon

doi:10.1055/s-0030-1260024

Cited by 12 publications

(3 citation statements)

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“…intermediate 599 , can be accessed by a double [2.3] sigmatropic rearrangement of the dipropargylic disulfide 598 . This heteroorganic bisallene subsequently cyclizes to the bicyclic product 600 , among other things, in a multistep tandem process of high atom economy [296–297]. Note the structural similarity of product 586 in Scheme 129 with that of 600 in Scheme 131.…”

Section: Reviewmentioning

confidence: 99%

The chemistry of bisallenes

Hopf¹,

Μαρκόπουλος²

2012

Beilstein J. Org. Chem.

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SummaryThis review describes the preparation, structural properties and the use of bisallenes in organic synthesis for the first time. All classes of compounds containing at least two allene moieties are considered, starting from simple conjugated bisallenes and ending with allenes in which the two cumulenic units are connected by complex polycyclic ring systems, heteroatoms and/or heteroatom-containing tethers. Preparatively the bisallenes are especially useful in isomerization and cycloaddition reactions of all kinds leading to the respective target molecules with high atom economy and often in high yield. Bisallenes are hence substrates for generating molecular complexity in a small number of steps (high step economy).

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Section: Reviewmentioning

confidence: 99%

The chemistry of bisallenes

Hopf¹,

Μαρκόπουλος²

2012

Beilstein J. Org. Chem.

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“…The diverse applicability of this type of molecules can be explained by the fact that the calcogen atom exerts a stabilizing effect on positive or negative neighboring charges that makes the double bond in vinyl chalcogenides susceptible of both nucleophilic and electrophilic attacks, an extremely useful resource for organic synthetic purposes. However, despite the fact that bis-vinyl-seleides compounds are very promising in biological and synthetic aspects, the methods applied until now for their synthesis are considerably outdated and aggressive from an environmental point of view As can be seen in scheme 1, the obtaining of this type of structure was carried out through a methodology with several disadvantages, such as the use of toxic solvents, reagentes, heavy metals and long reaction times [4][5][6].…”

Section: Introductionmentioning

confidence: 99%

Efficient Eco-Friendly Solvent-Free Obtaining Bis-Selenium-Alkenes with High Biological Potential

Cordeiro

Prado

Neto

et al. 2020

The 1st International Electronic Conference on Catalysis Sciences

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Organocalcogenides, in particular, organoselenium compounds have been widely studied due to the large number of synthetic and biological applications. Among organoselenium compounds, a class of bis-selenide-alkene derivatives has attracted attention. Recently, some studies have been developed to the synthesis of vinyl chalcogen derivatives, since these are also highly valuable intermediates in several synthetic applications. However, the methodologies developed so far have extensive reaction times, use of toxic solvents and heavy metals. Therefore, there is an emerging need to develop protocols for the synthesis of these molecules that are in accordance with the principles of green chemistry. In this work, we developed an alternative synthesis of bisselenium-alkene derivatives, through an environmentally appropriate methodology. Reaction optimization was evaluated from the diphenylacetylene and diphenyl diselenide, using I2/DMSO as a catalytic system under microwave irradiation or conventional heating. The variations of these conditions were carried out through different equivalences between the reagents, the amount of catalyst (I2), temperature, DMSO and the reaction process (MW or conventional). Even now, it was found that the best established condition was using diphenylacetylene, diphenyl diselenide, 30mol% I2 in DMSO, under microwave irradiation at 100°C for 10min. In this condition the product was obtained in 82% yield and its characterization was performed using 1H and 13C NMR spectroscopy. Therefore, the methodology that is being developed, in addition to perfectly attending to the principles of green chemistry, will allow to evaluate the reaction scope using different alkenes and diselenides or even disulfides and ditellurides.

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“…The study of reactivity of bis-propargyl sulfones, ethers, and sulfonamides has drawn interest in recent years . The reaction involves the formation of two C–C bonds in high yields under mild conditions, leading to the formation of an aromatic ring and is popularly known as Garratt–Braverman (GB) cyclization . The synthetic utility of the reaction has recently been elaborated in a series of publications .…”

Section: Introductionmentioning

confidence: 99%

Shifting the Reactivity of Bis-propargyl Ethers from Garratt–Braverman Cyclization Mode to 1,5-H Shift Pathway To Yield 3,4-Disubstituted Furans: A Combined Experimental and Computational Study

Das

Jana

et al. 2015

J. Org. Chem.

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Aryl or vinyl substituted bis-propargyl ethers upon base treatment generally form phthalans via the Garratt-Braverman (GB) cyclization pathway. In a major departure from this usual route, several aryl/vinyl bis-propargyl ethers with one of the acetylenic arms ending up with 2-tetrahydropyranyloxy methyl or ethoxy methyl have been shown to follow the alternative intramolecular 1,5-H shift pathway upon base treatment. The reaction has led to the formation of synthetically as well as biologically important 3,4-disubstituted furan derivatives in good yields. The initially formed E isomer in solution (CDCl3) slowly isomerizes to the Z isomer, indicating greater stability of the latter. The factors affecting the interplay between the 1,5-H shift and GB rearrangement have also been evaluated, and the results are supported by DFT-based computational study.

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Reactivity Pattern of Bis(propargyloxy) Disulfides: Tandem Rearrangements and Cyclizations

Cited by 12 publications

References 1 publication

The chemistry of bisallenes

The chemistry of bisallenes

Efficient Eco-Friendly Solvent-Free Obtaining Bis-Selenium-Alkenes with High Biological Potential

Shifting the Reactivity of Bis-propargyl Ethers from Garratt–Braverman Cyclization Mode to 1,5-H Shift Pathway To Yield 3,4-Disubstituted Furans: A Combined Experimental and Computational Study

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