Peristera Stamouli

Bio: Peristera Stamouli is an academic researcher. The author has contributed to research in topics: Diels–Alder reaction & Sigmatropic reaction. The author has an hindex of 2, co-authored 4 publications receiving 25 citations.

1,3-Butadienyl-thiocyanate in der Diels-Alder-Reaktion mit anschliessender [3,3]-sigmatroper Umlagerung

Abstract: 1,3-Butadienyl Thiocyanates in the Diels-Alder Reaction Followed by a [3,3]-Sigmatropic Shift (E)- and (Z)-1,3-Butadienyl thiocyanates 3, 4, and 12–15 have been synthesized selectively. Their use as dienes for Diels-Alder reactions followed by a [3,3]-sigmatropic shift to obtain an isomeric isothiocyanate has been studied. The butadienyl thiocyanates are, unfortunately, not very reactive in Diels-Alder reactions. This disadvantage can be overcome, if a trapping reaction with EtOH is added to the two-step sequence. This sequence allows to get good yields of the O-ethyl thiocarbamates 18–23, even if the first two reactions have not favorable equilibrium constants.

Synthesis of (E)- and (Z)-1-thiocyanatobuta-1,3-dienes and their Diels–Alder reaction

Abstract: 1-Thiocyanatobuta-1,3-dienes react with strong dienophiles to produce directly the rearranged products of type (6)via a combination of a Diels–Alder reaction with a [3,3] sigmatropic shift.

Synthesis of (e)- and (z)-1-thiocyanatobuta-1,3-dienes and their diels-alder reaction

Abstract: 1-Thiocyanatobuta-1,3-dienes react with strong dienophiles to produce directly the rearranged products of type (6)via a combination of a Diels–Alder reaction with a [3,3] sigmatropic shift.

Rearrangement Reactions, 6. New Functionalized Allenes: Synthesis Using Sigmatropic Rearrangements and Unusual Reactivity

Abstract: The present article summarizes the synthesis of allenes, which bear a functional group with at least two heteroatoms, by [2,3] or [3,3] sigmatropic rearrangements of appropriate propargyl precursors. Recently, this method has been extended to prepare new types of functionalized allenes such as isocyanates, isothiocyanates, isoselenocyanates, azides, thiocarbonates, and azo compounds. The title compounds are very reactive as shown by rapid intra- and intermolecular consecutive reactions. This reactivity can be used to synthesize heterocycles and doubly functionalized 1,3-butadienes.

Tandem Diels-Alder and retro-ene reactions of 1-sulfenyl- and 1-sulfonyl-1,3-dienes as a traceless route to cyclohexenes.

Abstract: A pericyclic approach for the synthesis of six-membered ring structures is described. The method employs 1,3-dienes with a 1-sulfur substituent in a tandem sequence of Diels–Alder and retro-ene reactions. In this pairing of [4 + 2] cycloaddition and 1,5-sigmatropic rearrangement, 1-sulfenyl-1,3-dienes engage in Diels–Alder reactions with electron-deficient dienophiles. Subsequently, the sulfenyl group of the cycloadducts is oxidized and unmasked to form allylic sulfinic acids, which undergo sterospecific reductive transposition via sulfur dioxide extrusion. The sequence can also include an inverse electron demand Diels–Alder reaction by using a 1-sulfonyl-1,3-diene. This combination of two pericyclic events offers novel stereocontrolled access to cyclohexenes that are inaccessible via a direct [4 + 2] cycloaddition route.

Lewis-acid catalysed tandem reaction Diels–Alder–[3,3] sigmatropic shift between buta-1,3-dienyl thiocyanic acid ester and acryloyl chloride: application in the synthesis of 2-azabicyclo[2.2.2]oct-5-ene derivatives

Abstract: Buta-1,3-dienyl thiocyanic acid ester reacts with acryloyl chloride in presence of Lewis acid catalysts to produce directly the rearranged product of type 3bvia a combination of a Diels-Alder reaction with a [3,3] sigmatropic shift; the 1,4-substituted cyclohexene is easily transformed into the 2-azabicyclo[2.2.2]oct-5-ene derivative 6b, which has been used as precursor for the synthesis of the Ibogamin skeleton.

Catalytic Asymmetric Diels-Alder Reaction/[3,3] Sigmatropic Rearrangement Cascade of 1-Thiocyanatobutadienes.

Abstract: A highly efficient asymmetric Diels-Alder/[3,3] sigmatropic rearrangement reaction of methyleneindolinones with 1-thiocyanatobutadienes has been realized by using a chiral N,N'-dioxide/nickel(II) complex as the catalyst. A range of cyclohexenyl isothiocyanates were synthesized in high yields with excellent diastereo- and enantioselectivities. Based on mechanistic studies, a catalytic cycle with possible transition-state models were proposed to explain the process.