Novel aspects of carbonyl oxide chemistry

Ishiguro, Katsuya; Nojima, Takayuki; Sawaki, Yasuhiko

doi:10.1002/(sici)1099-1395(199711)10:11<787::aid-pca948>3.0.co;2-1

Cited by 22 publications

(7 citation statements)

References 107 publications

(83 reference statements)

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“…The observation (ii) is as expected, since the reaction is generally more selective in crystals than in a solution. Scheme 3 describes another possible decomposition pathway (path b), where the cleavage of two C-O bonds occurs first and the ensuing carbonyl oxide intermediate, as recently described in a review [35], leads mainly to the formation of ester 3. It may be assumed that path b is occurring to some extent in the solution, since the 2/3 selectivity is low.…”

Section: Reactivity Of Trans-1 and Cis-1mentioning

confidence: 96%

Crystal structures and photoreactivity of trans- and cis-valerophenone diperoxides

Takahashi

Ito

2011

Struct Chem

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The crystal structures of valerophenone diperoxides trans-1 and cis-1 were elucidated by X-ray crystallographic analysis. The 1,2,4,5-tetraoxane rings of both compounds adopt chair conformations. Intermolecular CHÁÁÁO hydrogen bond, p-p, and CH/p interactions exist in cis-1, whereas only CH/p interactions exist in trans-1. In the asymmetric unit of the crystal, a half molecule exists for trans-1, while one molecule for cis-1 which shows wholemolecule disorder. Solid-state photolysis (at 254 nm) or solution-state thermolysis (at 150°C) of trans-1 and cis-1 produced valerophenone (2) and butyl benzoate (3). Rationalization of the solid-state photoreactivity of the diperoxides by their crystal structures was attempted.

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Section: Reactivity Of Trans-1 and Cis-1mentioning

confidence: 96%

Crystal structures and photoreactivity of trans- and cis-valerophenone diperoxides

Takahashi

Ito

2011

Struct Chem

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“…For reference, the lighter congener of dithiirane, dioxirane ( 1c ), can undergo homolytic O–O cleavage to yield dioxymethylene, which subsequently decomposes to furnish simpler downstream molecules such as CO 2 . Conversely, the Criegee intermediate ( 1b ) combines with formaldehyde ( 1d ) to generate the canonical product, 1,2,4-trioxolane ( 1e ) . It is likely that the sulfur analogues exhibit equally rich but unknown chemistry.…”

Section: Introductionmentioning

confidence: 99%

“…14 Conversely, the Criegee intermediate (1b) combines with formaldehyde (1d) to generate the canonical product, 1,2,4trioxolane (1e). 15 It is likely that the sulfur analogues exhibit equally rich but unknown chemistry.…”

Section: ■ Introductionmentioning

confidence: 99%

Thioformaldehyde S-Sulfide, Sulfur Analogue of the Criegee Intermediate: Structures, Energetics, and Rovibrational Analysis

et al. 2017

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The ephemeral Criegee intermediate, first postulated over 70 years ago, has only recently been isolated in the gas phase. The sulfur analogue of this canonical zwitterion, thioformaldehyde S-sulfide, has eluded similar analysis; however, argon matrix isolation has been achieved ( Angew. Chem., Int. Ed. 2001 , 40 , 393 - 396 ). Here thioformaldehyde S-sulfide and its valence isomer dithiirane are examined with high-level coupled-cluster methods, including the minimum-energy pathway for interconversion. Relative enthalpies calculated from extrapolated energies at the complete basis set limit of the full CCSDTQ method are reported. Isomerization from thioformaldehyde S-sulfide to the lower-lying dithiirane (-7.2 kcal mol) is predicted to include a 27.0 kcal mol barrier. Harmonic and anharmonic vibrational frequencies are also predicted using second-order vibrational perturbation theory. These results should aid in future gas-phase identification.

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“…VIII to IX ). Formation of 7 , on the other hand, can be rationalized by an intramolecular proton-transfer within the initially formed 1,3-zwitterion VIII and subsequent oxidation of the resulting carbene X by oxygen 12. This type of reactivity was earlier reported by Biju and coworkers 10 c .…”

Section: Resultsmentioning

confidence: 56%

Reactions of thermally generated benzynes with six-membered N-heteroaromatics: pathway and product diversity

et al. 2019

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We report here various pathways by which six-membered N-heteroaromatic compounds react with benzynes that are generated by the HDDA reaction. The initially formed 1,3-zwitterionic species (a) can collapse intramolecularly to give novel 1 : 1 adducts of the heterocycle and benzyne; (b) can react with an externally added, electrophilic third-component to give functionalized heterocyclic products; or (c) can react with an external protic nucleophile to produce, following collapse of the ion pair resulting from protonation of the zwitterion, a variety of three-component assemblies. Mechanisms for formation of some of the 1 : 1 adducts are supported by DFT methods. The scope of the protic nucleophilic coupling was also expanded to a two-pot operation by using triflic acid as a protic "non-nucleophile", followed by the addition of a suitably reactive nucleophile.

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Novel aspects of carbonyl oxide chemistry

Cited by 22 publications

References 107 publications

Crystal structures and photoreactivity of trans- and cis-valerophenone diperoxides

Crystal structures and photoreactivity of trans- and cis-valerophenone diperoxides

Thioformaldehyde S-Sulfide, Sulfur Analogue of the Criegee Intermediate: Structures, Energetics, and Rovibrational Analysis

Reactions of thermally generated benzynes with six-membered N-heteroaromatics: pathway and product diversity

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