Rhodium(II)‐Catalyzed Isomerization of Cyclopropenylmethyl Esters into (Acyloxymethylene)cyclopropanes

Archambeau, Alexis; Nguyen, Dinh-Vu; Meyer, Christophe; Cossy, Janine

doi:10.1002/chem.201505063

Cited by 11 publications

(5 citation statements)

References 114 publications

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“…In our previous report, the unsaturated bond of the coupling products having a protected hydroxyl group could be stereoselectively reduced by catalytic hydrogenation to provide the corresponding cis -cyclopropane derivatives. However, in the present study, hydrogenation of compound 22 possessing an unprotected alcohol, in the presence of Pd/C or Rh/C as catalysts, failed to give the desired cyclopropane and led instead to a complex mixture of products. On the other hand, diimide reduction of 22 using o -nitrobenzenesulfonyl hydrazide with Et 3 N produced the desired saturated alcohol 23 as a diasteromixture ( cis / trans = 1/0.8).…”

Section: Resultscontrasting

confidence: 68%

Synthesis of Chiral cis-Cyclopropane Bearing Indole and Chromone as Potential TNFα Inhibitors

et al. 2018

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Conformationally restricted analogues of SPD-304, the first small-molecule TNFα inhibitor, in which two heteroaryl groups, indole and chromone, are connected by chiral methyl- or ethyl- cis-cyclopropane, were designed. Synthesis of these molecules was achieved via Suzuki-Miyaura or Stille coupling reactions with chiral bromomethylenecyclopropane or iodovinyl- cis-cyclopropane as the substrate, both of which were prepared from chiral methylenecyclopropane as a common intermediate, constructing the heteroaryl-methyl or -ethyl- cis-cyclopropane structures as key steps. This study presents an efficient synthesis of a series of chiral cis-cyclopropane conjugates with two heteroaryl groups.

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Section: Resultscontrasting

confidence: 68%

Synthesis of Chiral cis-Cyclopropane Bearing Indole and Chromone as Potential TNFα Inhibitors

et al. 2018

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“…We chose to use the “solvent-free” conditions to study the scope of the GaCl 3 -catalyzed reaction, which is shown in Table . The E / Z ratio of the enol acetates is indicated, but since they are meant to be converted into the corresponding aldehydes, , this point is not essential. Diacetoxypropene 1a was first used as acceptor (entries 1–13).…”

supporting

confidence: 77%

“…The decrease in yield compared to Table , entry 14, can be explained by an increase of temperature when working at such a scale. Methanolysis led to the β-aryl aldehyde 3m , which decomposes rapidly when stored at rt. It was rapidly engaged in a Horner–Wadsworth–Emmons reaction, which provided dianethole in 42% yield.…”

mentioning

confidence: 99%

Gallium-Catalyzed Scriabine Reaction

2018

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γ-Aryl enol acetates are easily obtained from diacetoxy alkenes and electron-rich arenes at room temperature using GaCl 3 as catalyst. The products can then be converted into β-aryl aldehydes. This method represents the first broadly applicable catalytic version of the Scriabine reaction. DFT computations shed light on the mechanism of this transformation.β-Aryl-saturated aldehydes (dihydrocinnamaldehydes) are of fundamental interest in organic chemistry, as they are used as synthons in the preparation of natural products and pharmaceuticals or as ingredients of fragrances. 1 Various strategies have been reported to synthesize such compounds, but the most obvious route, the Michael addition of arenes to α,β-unsaturated aldehydes, remains a difficult task (eq 1). 2

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“…Only a few compounds of this family had been previously generated by photochemical reactions (from 4-isopropylidene-3,3-dimethyl-1-thietan-2-thione [38] or from a 4-alkylidene-Δ 1 -pyrazoline [39]) or by pyrolysis of the sodium salt of 3-propionyloxytetramethylcyclobutanone tosyl hydrazone [40]. It is also worth mentioning that completely divergent reactivities have also been reported for cyclopropenylcarbinyl esters in the presence of transition metal catalysts [41–42].…”

Section: Reviewmentioning

confidence: 99%

Sigmatropic rearrangements of cyclopropenylcarbinol derivatives. Access to diversely substituted alkylidenecyclopropanes

Ernouf¹,

Brayer²,

Meyer³

et al. 2019

Beilstein J. Org. Chem.

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Cyclopropenes constitute useful precursors of other classes of compounds incorporating a three-membered ring. Although the transformation of substituted cyclopropenes into alkylidenecyclopropanes can be accomplished through different strategies, this review is focusing specifically on the use of [2,3]- and [3,3]-sigmatropic rearrangements involving cyclopropenylcarbinol derivatives as substrates. These sigmatropic rearrangements, which have been developed in recent years, allow a remarkably efficient and stereoselective access to a wide variety of heterosubstituted and/or functionalized alkylidenecyclopropanes which would not be readily accessible by other strategies. The different [2,3]- and [3,3]-sigmatropic rearrangements of cyclopropenylcarbinol derivatives disclosed to date, as well as the analysis of their substrate scope and some applications of the products arising from those reactions, are presented in this review.

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Rhodium(II)‐Catalyzed Isomerization of Cyclopropenylmethyl Esters into (Acyloxymethylene)cyclopropanes

Cited by 11 publications

References 114 publications

Synthesis of Chiral cis-Cyclopropane Bearing Indole and Chromone as Potential TNFα Inhibitors

Synthesis of Chiral cis-Cyclopropane Bearing Indole and Chromone as Potential TNFα Inhibitors

Gallium-Catalyzed Scriabine Reaction

Sigmatropic rearrangements of cyclopropenylcarbinol derivatives. Access to diversely substituted alkylidenecyclopropanes

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