[1,3], [3,3], and [3,5] Sigmatropic Rearrangements of Esters Are Pseudopericyclic

Birney, David M.; Xu, Xiaolian; Ham, Sihyun

doi:10.1002/(sici)1521-3773(19990115)38:1/2<189::aid-anie189>3.3.co;2-m

Cited by 11 publications

(19 citation statements)

References 2 publications

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“…On the other hand, the [1,3′] isomers could result from a fragmentation-recombination mechanism or, alternatively, from an allowed concerted pseudopericyclic process similar to that observed in the rearrangement of allylic esters. 24,25 There are then still many open questions regarding the isomerization of allylsacharyl ethers, which deserve further investigation. In the present paper, we report the results of our studies on the thermal isomerization of 3-(allyloxy)-1,2-benzisothiazole 1,1-dioxide (ABID; Scheme 1) using a concerted methodological approach, in which temperature dependent infrared spectroscopy, differential scanning calorimetry, and polarized light thermomicroscopy were used, complemented by theoretical methods.…”

Section: Introductionmentioning

confidence: 99%

Thermally Induced Sigmatropic Isomerization of Pseudosaccharyl Allylic Ether

et al. 2009

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The thermally induced sigmatropic isomerization of the pseudosaccharyl allylic ether [3-(allyloxy)-1,2-benzisothiazole 1,1-dioxide; ABID] has been investigated by a multidisciplinary approach using temperature dependent infrared spectroscopy, differential scanning calorimetry, and polarized light thermomicroscopy, complemented by theoretical methods. Migration of the allylic system from O to N occurs in the melted ABID, and the thermally obtained 2-allyl-1,2-benzisothiazol-3(2H)-one 1,1-dioxide (ABIOD) starts to be produced at ca. 150 °C, in a process with an activation energy of ∼92 kJ mol−1. From kinetic data, a concerted [3,3′] sigmatropic mechanism is proposed. In the temperature range investigated, ABIOD was found to exhibit polymorphism. Cooling of the molten compound leads to the production of a metastable crystalline form, which upon annealing at room temperature might be transformed to the stable crystalline phase. ABID shows a single crystalline variety. Assignments were proposed for the infrared spectra of the observed neat condensed phases of the two compounds.

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Section: Introductionmentioning

confidence: 99%

Thermally Induced Sigmatropic Isomerization of Pseudosaccharyl Allylic Ether

et al. 2009

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“…According to Birney et al [4][5][6][7][8], pseudopericyclic reactions have planar or nearly planar transition states and small reaction barrier. Fig.…”

Section: Pseudopericyclic Reactionmentioning

confidence: 99%

“…There are three types of pericyclic reactions cycloaddition, sigmatropic migration reactions and electrocyclic reactions. In some pericyclic reaction non-bonding electron also takes part in the cyclic transition state such reaction called pseudopericyclic reactions [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18]. Since no absolute criteria exists for distinguishing a pseudopericyclic reaction from a pericyclic one some reactions are difficult to classify [19][20][21][22][23].…”

Section: Introductionmentioning

confidence: 99%

Ab initio molecular orbital and density functional studies on the ring-opening reaction of 2H-thiete

Jayaprakash¹,

Jeevanandam²,

Subramani³

et al. 2015

Computational and Theoretical Chemistry

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“…[189][190][191][192] The effects of fluorine-containing substituents upon the torquoselectivity in the monorotatory process during these reactions can be seen through the relative rates of electrocyclizations of the E and the Z isomers of 163c,d and 163f (Table 9). 188 The ratios show that the torquoselectivities are not steric in origin, since the largest effect originates from the smallest, fluoro substituent, whereas the smallest kinetic effect is seen from a large trifluoromethyl group.…”

Section: Fluoroorganic Compounds In Theoretical Studiesmentioning

confidence: 99%