On the mechanism of the sensitized photooxygenation of pyrroles

Lightner, David A.; Bisacchi, Gregory S.; Norris, Robert D.

doi:10.1021/ja00419a029

Cited by 54 publications

(20 citation statements)

References 2 publications

(4 reference statements)

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“…This slower reaction rate in acetone results in lower yields as well as more complex reaction mixtures, which includes cleavage of the ring. Lightner and co‐workers carried out mechanistic studies using low temperature 1 H NMR spectroscopy and 18 O incorporation experiments . From these experiments they concluded that while competing [2+2]‐cycloaddition reaction across C2 and C3 was possible, it was more likely that reactions in acetone were proceeding through rearrangement of the endo ‐peroxide formed in the [4+2] process.…”

Section: Oxidation Of Pyrrole With Singlet Oxygenmentioning

confidence: 99%

The Oxidation of Pyrrole

Howard

Rihak

Bissember

et al. 2015

Chemistry An Asian Journal

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The dearomatization of heterocycles has been a powerful means for producing functional molecules in synthesis. In the case of pyrroles, reductive methods (such as the Birch reduction) have been most widely exploited, while oxidative methods are generally dismissed as too difficult or unpredictable to be useful. However, since the early twentieth century considerable research has been carried out on the controlled oxidation of pyrroles to give highly functionalized products, using a variety of oxidants. This review presents a summary of all work up until the present day in the area of pyrrole oxidation, looking at the use of peroxide, singlet oxygen, hypervalent iodine reagents, a range or organic and inorganic oxidants, and electrochemical approaches. It also offers some perspective on the potential future role of pyrrole oxidation in synthesis.

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Section: Oxidation Of Pyrrole With Singlet Oxygenmentioning

confidence: 99%

The Oxidation of Pyrrole

Howard

Rihak

Bissember

et al. 2015

Chemistry An Asian Journal

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“…As shown in Scheme 1, the charge transfer complex is postulated to be in equilibrium with an endoperoxide intermediate. Such endoperoxides are believed to be intermediates in the photochemical dye-sensitized oxidation of pyrroles [24]. Such a common intermediate for both sensitized photoxidation and autoxidation could thus account for the observation that many photochemical oxidations and autoxidations produce the same type of oxidation products [25,26,27].…”

Section: Imentioning

confidence: 99%

Autoxidation of nitrogen heterocycles. 3. Solvent effects in the autoxidation of 2,5‐dimethylpyrrole

Beaver

Cooney

Watkins

1986

Journal of Heterocyclic Chem

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“…This mechanism can be facilitated by the low oxidation potential of amine. Precedents for this finding were obtained by Lightner et al, 11,23 who identified hydroxyketones among the products of photooxygenated pyrroles. An internal rearrangement was suggested as a putative mechanism, since the decomposition did not involve any addition of solvent (hydroxyketones were formed even in the absence of water, pointing to a minor role of hydrolysis).…”

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confidence: 83%