The thermal .beta.-cis-elimination reaction of cyclic sulfoxides and subsequent ring expansion reactions

Janssen, Johann; Kwart, Harold

doi:10.1021/jo00429a011

Cited by 35 publications

(18 citation statements)

References 2 publications

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“…Dehydroalanine formation likely results from the elimination of a sulfur-nitrogen intermediate or the final sulfinamide (Pathway A). Direct amination of cysteine residues yields dehydroalanaine and the loss of HOSNH 2 from the sulfinamide finds some precedent in sulfoxide eliminations to yield alkenes [37-40, 43]. Regardless of the mechanism, the formation of dehydroalanine from the reaction of HNO and thiol-containing peptides indicates new HNO chemistry that may be exploited for HNO detection.…”

Section: Resultsmentioning

confidence: 99%

Water soluble acyloxy nitroso compounds: HNO release and reactions with heme and thiol containing proteins

DuMond

Wright

King

2013

Journal of Inorganic Biochemistry

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Nitroxyl (HNO) has gained interest as a potential treatment of congestive heart failure through the ability of the HNO donor, Angeli’s salt (AS), to evoke positive inotropic effects in canine cardiac muscle. The release of nitrite during decomposition limits the use of AS requiring other HNO sources. Acyloxy nitroso compounds liberate HNO and small amounts of nitrite upon hydrolysis and the synthesis of the water-soluble 4-nitrosotetrahydro-2H-pyran-4-yl acetate and pivalate allows for pig liver esterase (PLE)-catalysis increasing the rate of decomposition and HNO release. The pivalate derivative does not release HNO, but the addition of PLE catalyzes hydrolysis (t1/2 = 39 min) and HNO formation (65% after 30 min). In the presence of PLE, this compound converts metmyoglobin (MetMb) to iron nitrosyl Mb and oxyMb to metMb indicating these compounds only react with heme proteins as HNO donors. The pivalate in the presence and the absence of PLE inhibits aldehyde dehydrogenase (ALDH) with IC50 values of 3.5 and 3.3 μM, respectively, in a time-dependent manner. Reversibility assays reveal reversible inhibition of ALDH in absence of PLE and partially irreversible inhibition with PLE. Liquid chromatography-mass spectrometry (LC-MS) reveals formation of a disulfide upon incubation of an ALDH peptide without PLE and a mixture of disulfide and sulfinamide in the presence of PLE. A dehydroalanine residue forms upon incubation of this peptide with excess AS. These results identify acyloxy nitroso compounds as unique HNO donors capable of thiol modification through direct electrophilic reaction or HNO release.

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Section: Resultsmentioning

confidence: 99%

Water soluble acyloxy nitroso compounds: HNO release and reactions with heme and thiol containing proteins

DuMond

Wright

King

2013

Journal of Inorganic Biochemistry

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“…The second fraction furnished the ligand-exchange product 4,4-dimethyl-2-(naphthalen-2-yl)-4,5-dihydrooxazole 9 (57 mg, 44%) as an oil, which was identified by its 'H NMR spectrum. 43 The third fraction furnished thephenylnuphthalene 10 (60 mg, 35%) as an oil (Found: (34), 244 (23), 242 (21), 230 (30), 229 (loo), 227 (31) and 202 (34).…”

Section: 4-dimethyl-2-( 1 -Phenylnaphthalen-2-yl)-45-dihydrooxazole 10mentioning

confidence: 99%

“…Work-up after 15 min in the usual way gave a crude product, which was purified by radial chromatography with 30% ethyl acetate-light petroleum as eluent. This afforded the sulfoxide 19 (23), 202 (36), 160 (27), 153 (22), 146(81), 140 (38), 133 (21), 132 (50), 126 (23), 118 (66), 106 (31) and 105 (71).…”

Section: (S)-44-dimethyl-2-{ 1-[(4methylphenyl)sulfinyl]naphthalen-2-...mentioning

confidence: 99%

Atropisomer-selective ligand-coupling reactions of sulfoxides. X-Ray molecular and crystal structures for 2-({2-(4-chlorophenyl)naphtho[1,2-b]thiophen-3-yl}amino)-2-methylpropan-1-ol, 2-(2-hydroxy-1,1-dimethylethyl)-2,3-dihydronaphtho[2,1-d]isothiazol-3-one and (R)-(+)-2-bromo-1-(tert-butylsulfinyl)naphthalene

Baker¹,

Hockless²,

Pocock³

et al. 1995

J. Chem. Soc., Perkin Trans. 1

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“…[2][3][4][5][6][7][8] Kinetic investigations for the Ei reaction of the sulfoxides have revealed that both C S bond fission and β-proton transfer are important, and thus a concerted mechanism has been suggested from the observations of positive Hammett ρ-values 8,9 for the substituent effect on the S-phenyl group and large deuterium kinetic isotope effects on β-position. 10,11 However, we recently demonstrated that the transition state is variable depending on the substituent on the α-or β-position of the sulfoxides. For example, introduction of a phenyl group on the α-position of ethyl phenyl sulfoxide causes the transition state to deviate to one in which the C S bond cleavage is more progressed than proton transfer, that is, a partially positive charge is developed on the α-carbon (E1-like).…”

Section: Introductionmentioning

confidence: 99%

Pyrolysis of α- and β-Heteroatoms Substituted Ethyl Phenyl Sulfoxides

Yoshimura

Sakae

Yoshizawa

et al. 2010

Phosphorus, Sulfur, and Silicon and the Related Elements

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A study on the mechanism of the thermal decomposition of α-and β-heteroatoms substituted ethyl phenyl sulfoxides was carried out using 1-chloroethyl phenyl sulfoxide (1); two diastereomeric 1-acetoxyethyl (substituted phenyl) sulfoxides (2a) and (2b); and 2-chloroethyl phenyl, 2-bromoethyl phenyl, and 2-methoxyethyl phenyl sulfoxides (3, 4, 5). The rate of pyrolysis of 1 was 4.8 times faster at 160 • C than that of ethyl phenyl sulfoxide used as a reference, while those of 2a and 2b were 107 and 155 times faster, respectively. The results indicate that the lone pair of electrons on the α-heteroatoms has a larger rate acceleration effect than the electronegativity of them. The substituent effects of the phenyl group of 2a and 2b gave positive Hammett ρ-values (ρ a = 0.76 and ρ b = 0.80 vs. σ ). Activation parameters for 2a and 2b are as follows: 2a, H ‡ = 112 kJmol −1 , S ‡ = −20 JK −1 mol −1 ; 2b, H ‡ = 107 kJmol −1 , S ‡ = −29 JK-1mol −1 .Large deuterium kinetic isotope effects for 1-acetoxyethyl-2,2,2-d 3 phenyl sulfoxides (2ad and 2bd) were observed (k H /k D = 3.5 ∼ 4.1). These results suggest that the pyrolysis of α-heteroatom substituted ethyl phenyl sulfoxides proceeds via a five-membered transition state deviated to E1-like in character. On the other hand, from the results of kinetics for the pyrolysis of 3, 4, and 5, no effect by the β-halogen atoms or some deceleration effect by the β-methoxy group was observed. Thus the reaction seems to proceed via an E1-like mechanism.

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The thermal .beta.-cis-elimination reaction of cyclic sulfoxides and subsequent ring expansion reactions

Cited by 35 publications

References 2 publications

Water soluble acyloxy nitroso compounds: HNO release and reactions with heme and thiol containing proteins

Water soluble acyloxy nitroso compounds: HNO release and reactions with heme and thiol containing proteins

Pyrolysis of α- and β-Heteroatoms Substituted Ethyl Phenyl Sulfoxides

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