Photoinduced Free Radical Chemistry of the Acyl Tellurides: Generation, Inter- and Intramolecular Trapping, and ESR Spectroscopic Identification of Acyl Radicals

Crich, David; Chen, Chen; Hwang, Jae‐Taeg; Hu, Yuan; Papadatos, Aristotle; Walter, Robert I.

doi:10.1021/ja00099a011

Cited by 144 publications

(72 citation statements)

References 4 publications

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“…[11]), its norethyl derivative (12, for synthesis, see the Supporting Information), trans-(1-phenyl)but-2-en-1-one (9, Sigma-Aldrich), 3-methylenechroman-4-one (10, synthesized according to ref. [38]), and 6-chloro-4H-chromen-4-one (11,Maybridge). The structures of these compounds are shown in Figure 3.…”

Section: Chemoassaysmentioning

confidence: 99%

Mechanistic Study of the Reaction of Thiol‐Containing Enzymes with α,β‐Unsaturated Carbonyl Substrates by Computation and Chemoassays

Paasche¹,

Schiller²,

Schirmeister³

et al. 2010

ChemMedChem

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We investigated the reactions between substituted alpha,beta-unsaturated carbonyl compounds (Michael systems) and thiols by computations as well as chemoassays. The results give insight into variations in the underlying mechanisms as a function of the substitution pattern. This is of interest for the mechanisms of inhibition of the SARS coronavirus main protease (SARS-CoV M(pro)) by etacrynic acid derivatives as well as for the excess toxicity of substituted alpha,beta-unsaturated carbonyl compounds. This study compares possible reaction courses including 1,4-addition followed by a ketonization step, and underscores the importance of a base-catalyzed step for the reactivity of thiol groups in enzymes. Phenyl and methyl substituents at the Michael system decrease the reactivity of the electrophilic compound, but chlorophenyl substituents partly recover the reactivity. Computations also indicate that electron-pushing substituents lead to a change in the reaction mechanism. The conformation of the Michael system is also found to significantly influence reactivity: the s-cis conformation leads to higher reactivity than the s-trans conformation. The computed data explain the trends in measured inhibition potencies of substituted alpha,beta-unsaturated carbonyl compounds and of reaction rates in chemical assays. They also indicate that the reversibility of inhibition does not stand in contrast to the formation of a new covalent bond between inhibitor and protease.

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Section: Chemoassaysmentioning

confidence: 99%

Mechanistic Study of the Reaction of Thiol‐Containing Enzymes with α,β‐Unsaturated Carbonyl Substrates by Computation and Chemoassays

Paasche¹,

Schiller²,

Schirmeister³

et al. 2010

ChemMedChem

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“…1 As a chain-carrying reagent, tributyltin hydride is cheap, readily available and has favourable rate constants for delivery of hydrogen atom to carbon-centred and other radicals [2][3][4][5][6] while the corresponding stannyl radical reacts readily with a variety of free-radical precursors. [6][7][8][9][10][11][12][13][14][15] The ability to establish free-radical chain reactions of synthetic utility is a direct result of recent significant advances made in our understanding of the factors which govern radical reactivity [16][17][18][19][20] together with a knowledge of the important rate constants involved in the overall chain process. [1][2][3][4][5][6] Formation of carbon-carbon bonds through the use of inter-and intramolecular homolytic addition chemistry 1,21 and carbon-heteroatom bonds through the use homolytic substitution chemistry 19 are key chemical reactions of synthetic significance which directly compete with hydrogen abstraction processes from chain carriers such as tributyltin hydride.…”

Section: Introductionmentioning

confidence: 99%

Steric trends and kinetic parameters for radical reductions involving alkyldiphenyltin hydrides

Dakternieks

Henry

Schiesser

1999

J. Phys. Org. Chem.

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Absolute rate constants and Arrhenius parameters for hydrogen atom abstraction by primary alkyl radicals from methyldiphenyl-, ethyldiphenyl-, butyldiphenyl-, isopropyldiphenyl-, cyclohexyldiphenyl-and (trimethylsilyl)methyldiphenyltin hydride were determined in tert-butylbenzene through utilization of the '5-hexenyl radical clock' reaction. At 80°C, rate constants (k H ) for all hydrides were found to lie in the range (8.2-11.5) Â 10

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“…Ferreira 3 studied the photodegradation process for arylbenzyltellurides. All this results indicates that the processes must be mediated by one or more radicalar steps [2] . On the other hand radical tellurides derivatives have considerable potential for use in organic synthesis [4,5] .…”

Section: Introductionmentioning

confidence: 78%

“…The photooxidation products of di-benzyl-tellurides and arylalkyl tellurides were described by Cava [1] and Clive 2 . Ferreira 3 studied the photodegradation process for arylbenzyltellurides.…”

Section: Introductionmentioning

confidence: 99%

Study of photo-degradation of new 2-oxazoline telluride derivative.

Oliveira

Mello²

2013

Proceedings of the 14th Brazilian Meeting on Organic Synthesis Proceedings

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Photoinduced Free Radical Chemistry of the Acyl Tellurides: Generation, Inter- and Intramolecular Trapping, and ESR Spectroscopic Identification of Acyl Radicals

Cited by 144 publications

References 4 publications

Mechanistic Study of the Reaction of Thiol‐Containing Enzymes with α,β‐Unsaturated Carbonyl Substrates by Computation and Chemoassays

Mechanistic Study of the Reaction of Thiol‐Containing Enzymes with α,β‐Unsaturated Carbonyl Substrates by Computation and Chemoassays

Steric trends and kinetic parameters for radical reductions involving alkyldiphenyltin hydrides

Study of photo-degradation of new 2-oxazoline telluride derivative.

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