Tandem Payne/Meinwald versus Meinwald rearrangements on the α-hydroxy- or α-silyloxy-spiro epoxide skeleton

Totobenazara, Jane; Rémond, Julien; Adil, Karim; Dénès, Fabrice; Lebreton, Jacques; Gaulon‐Nourry, Catherine; Gosselin, Pascal

doi:10.1039/c1ob06776a

Cited by 14 publications

(3 citation statements)

References 58 publications

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“…Isomeric MBO epoxides are possible in the chamber and field studies (Figure S3 of the Supporting Information, proposed oxidation pathway), and consistent with this possibility, three peaks are resolved in organosulfate EICs C2 and C3. Because the reactive uptake of pure (3,3-dimethyloxiran-2-yl)methanol should initially yield two sulfate isomers, the presence of three isomeric esters in C1 likely suggests either an initial Payne rearrangement , of the epoxide on reactive uptake or intramolecular transesterification , promoted by the acidic seed aerosol may be involved in reactive uptake. Differences in the pattern of peak intensities of the EIC traces in Figure are expected because isomer ratios from aerosol generated under different conditions are not anticipated to be identical.…”

Section: Resultsmentioning

confidence: 99%

Secondary Organic Aerosol Formation via 2-Methyl-3-buten-2-ol Photooxidation: Evidence of Acid-Catalyzed Reactive Uptake of Epoxides

Zhang

Cui

et al. 2014

Environ. Sci. Technol. Lett.

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Secondary organic aerosol (SOA) formation from 2-methyl-3-buten-2-ol (MBO) photooxidation has recently been observed in both field and laboratory studies. Similar to the level of isoprene, the level of MBO-derived SOA increases with elevated aerosol acidity in the absence of nitric oxide; therefore, an epoxide intermediate, (3,3-dimethyloxiran-2-yl)methanol (MBO epoxide), was synthesized and tentatively proposed to explain this enhancement. In this study, the potential of the synthetic MBO epoxide to form SOA via reactive uptake was systematically examined. SOA was observed only in the presence of acidic aerosol. Major SOA constituents, 2,3-dihydroxyisopentanol and MBO-derived organosulfate isomers, were chemically characterized in both laboratory-generated SOA and in ambient fine aerosol collected from the BEACHON-RoMBAS field campaign during the summer of 2011, where MBO emissions are substantial. Our results support the idea that epoxides are potential products of MBO photooxidation leading to the formation of atmospheric SOA and suggest that reactive uptake of epoxides may explain acid enhancement of SOA observed from other biogenic hydrocarbons.

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Section: Resultsmentioning

confidence: 99%

Secondary Organic Aerosol Formation via 2-Methyl-3-buten-2-ol Photooxidation: Evidence of Acid-Catalyzed Reactive Uptake of Epoxides

Zhang

Cui

et al. 2014

Environ. Sci. Technol. Lett.

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“…The α-hydroxy oxirane structural motif may shed light on the stereochemistry as illustrated in Figure 6. The C1 OH can interact with the incipient C2 carbonium ion in the transition state, which is similar to that of an acid-catalyzed Payne rearrangement, 111 and the C4 hydroxy substituent can interact with the oxirane oxygen through hydrogen bonds with or without an intervening water molecule. This transition state could direct the approach of sulfate and result in predominance of either retention or inversion of optical configuration at C2.…”

Section: Reaction Mechanism and Kineticsmentioning

confidence: 94%

Organosulfates from Dark Aqueous Reactions of Isoprene-Derived Epoxydiols Under Cloud and Fog Conditions: Kinetics, Mechanism, and Effect of Reaction Environment on Regioselectivity of Sulfate Addition

Petters

Cui

Zhang

et al. 2021

ACS Earth Space Chem.

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Atmospheric oxidation of isoprene yields large quantities of highly water-soluble isoprene epoxydiols (IEPOX) that partition into fogs, clouds, and wet aerosols. In aqueous aerosols, the acid-catalyzed ring-opening of IEPOX followed by nucleophilic addition of inorganic sulfate or water forms organosulfates and 2-methyltetrols, respectively, contributing substantially to secondary organic aerosol (SOA). However, the fate of IEPOX in clouds, fogs, and evaporating hydrometeors is not well understood.Here we investigate the rates, product branching ratios, and stereochemistry of organosulfates from reactions of dilute IEPOX (5−10 mM) under a range of sulfate concentrations (0.3−50 mM) and pH values (1.83−3.38) in order to better understand the fate of IEPOX in clouds and fogs. From these aqueous dark reactions of β-IEPOX isomers (trans-and cis-2-methyl-2,3-epoxybutane-1,4-diols), which are the predominant IEPOX isomers, products were identified and quantified using hydrophilic interaction liquid chromatography coupled to an electrospray ionization high-resolution quadrupole time-of-flight mass spectrometer operated in negative ion mode (HILIC/(−)ESI-HR-QTOFMS). We found that the regiochemistry and stereochemistry were affected by pH, and the tertiary methyltetrol sulfate (C 5 H 12 O 7 S) was promoted by increasing solution acidity. Furthermore, the rate constants for the reaction of IEPOX under cloud-relevant conditions are up to 1 order of magnitude lower than reported in the literature for aerosol-relevant conditions due to a markedly different solution activities. Nevertheless, the contribution of cloud and fog water reactions to IEPOX SOA may be significant in cases of lower aqueous-phase pH (model estimate) or during droplet evaporation (not studied).

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“…In 2012, Gosselin et al reported the Lewis acid-induced tandem Payne/Meinwald rearrangement of a-hydroxyl-spiro epoxide 121, which gave ketone 123 as the single product in the presence of Yb(OTf) 3 , BF 3 OEt 2 , or SnCl 4 (equation 12). 95 This tandem procedure began with the acid-induced Payne rearrangement of substrate 121, followed by a ring contraction of the resulting intermediate 122 to furnish stereospecifically the ketone 123. …”

Section: Side Reactionmentioning

confidence: 99%

3.16 The Semipinacol Rearrangements

Wang¹,

Tu²,

Tang³

2014

Comprehensive Organic Synthesis II

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Tandem Payne/Meinwald versus Meinwald rearrangements on the α-hydroxy- or α-silyloxy-spiro epoxide skeleton

Cited by 14 publications

References 58 publications

Secondary Organic Aerosol Formation via 2-Methyl-3-buten-2-ol Photooxidation: Evidence of Acid-Catalyzed Reactive Uptake of Epoxides

Secondary Organic Aerosol Formation via 2-Methyl-3-buten-2-ol Photooxidation: Evidence of Acid-Catalyzed Reactive Uptake of Epoxides

Organosulfates from Dark Aqueous Reactions of Isoprene-Derived Epoxydiols Under Cloud and Fog Conditions: Kinetics, Mechanism, and Effect of Reaction Environment on Regioselectivity of Sulfate Addition

3.16 The Semipinacol Rearrangements

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