Synthesis and use of cyclic peroxides

McCullough, Kevin J.

doi:10.1039/co9950200225

Cited by 29 publications

(15 citation statements)

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“…Although, several reviews on the synthesis of 1,2‐dioxetanes and 1,2‐dioxetanones are available, there is no report on the isolation of 1,2‐dioxetanodione ( 3 ). This elusive peroxide can be produced in situ by the reaction of oxalyl chloride with hydrogen peroxide and is often referred to as a high‐energy intermediate (HEI, protocol 2.1.4).…”

Section: The (Bio)chemistry Of Four‐membered Ring Peroxidesmentioning

confidence: 99%

“…Therefore, comments and insights are provided at the end of every procedure. More in‐depth details can be found in excellent revisions published elsewhere …”

Section: Experimental Protocolsmentioning

confidence: 99%

“…These compounds should always be prepared and handled in the minimum amounts possible and used directly in the preparation of the 1,2‐dioxetanes; if necessary, solutions in inert organic solvents (eg, dichloromethane and diethyl ether) can be stored for longer periods. 1,2‐Dioxetanes, specifically the low molecular weight derivatives, are definitively explosive . An explosion occurred in W. Adam's laboratory when a sample of impure 3,3‐dimethyl‐1,2‐dioxetane (around 500 mg) was transported to the freezer, resulting in a roughly 10‐cm diameter hole in the horizontal freezer door, but without serious personal damage.…”

Section: Experimental Protocolsmentioning

confidence: 99%

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Four‐membered cyclic peroxides: Carriers of chemical energy

Bastos

Farahani

Bechara

et al. 2017

J of Physical Organic Chem

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Four-membered cyclic peroxides are high-energy compounds often associated to cold light emission, but whose chemical and biological roles are still matters of debate. The often-dangerous synthesis of 1,2-dioxetanes, achieved around 50 years ago, has been mastered over the years to a point where some derivatives are commercially available. This fact does not imply that 1,2-dioxetanes can be conveniently prepared in the gram scale or that the synthesis of analogous 1,2-dioxetanones and the elusive 1,2-dioxetanedione are simple. Important questions on the mechanism of chemiluminescence and bioluminescence reactions are under experimental and theoretical scrutiny. The available data have contributed to relate structural and medium effects to the quantum efficiency of these compounds to produce excited states. Consequently, such peroxides have been suggested to produce biologically relevant electronically excited species in vivo in the absence of light. The connection of this hypothesis with melanin-mediated photodamage in the dark has renewed the interest in such cyclic peroxides. This review gives some insight on the synthesis, chemiluminescence mechanism, and biological relevance of 1,2-dioxetanes, 1,2-dioxetanones, and 1,2-dioxetanedione and provides practical protocols for those interested in engaging this field.

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Section: The (Bio)chemistry Of Four‐membered Ring Peroxidesmentioning

confidence: 99%

“…Therefore, comments and insights are provided at the end of every procedure. More in‐depth details can be found in excellent revisions published elsewhere …”

Section: Experimental Protocolsmentioning

confidence: 99%

Section: Experimental Protocolsmentioning

confidence: 99%

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Four‐membered cyclic peroxides: Carriers of chemical energy

Bastos

Farahani

Bechara

et al. 2017

J of Physical Organic Chem

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“…With the increasing frequency of isolation of cyclic peroxides from natural sources [ 391 and the demonstrable antiparasitic and many other biological properties possessed by both the natural products and their analogs, there is currently considerable interest in the synthesis of such compounds [5]. In particular, the opportunity of exploiting the facile conversion of enols or enolates into peroxyl radicals and then inducing cyclization of the peroxyl radical (or hydroperoxide) by addition to a distal carbonyl group is apparent.…”

Section: Preparation Of Cyclic Peroxidesmentioning

confidence: 99%

“…A book exclusively devoted to the latter topics has recently been published [l]. Some preparatively relevant pathways involving peroxyl radicals have been previously discussed in the context of reviews on the oxidation of organic molecules [2-41 and the synthesis of organic peroxides [5][6][7][8]. The present survey is clearly distinguished in scope; it is intended to cover a more diverse array of peroxyl radical pathways and to highlight recent applications in the field of natural product synthesis.…”

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confidence: 99%

Peroxyl Radicals in Synthesis

Boukouvalas¹,

Haynes²

2001

Radicals in Organic Synthesis

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This chapter covers organic compounds prepared via intermediates which are alkyl peroxyl radicals (ROO') generated either by addition of ground state (triplet) oxygen to carbon-centered radicals, or by hydrogen atom abstraction from the corresponding hydroperoxides (ROOH). While some earlier work is briefly mentioned, the focus is primarily on new developments, published over the past decade or so. The emphasis is heavily on synthetic applications rather than physical, biological and environmental aspects of peroxyl radical chemistry. A book exclusively devoted to the latter topics has recently been published [l]. Some preparatively relevant pathways involving peroxyl radicals have been previously discussed in the context of reviews on the oxidation of organic molecules [2-41 and the synthesis of organic peroxides [5][6][7][8]. The present survey is clearly distinguished in scope; it is intended to cover a more diverse array of peroxyl radical pathways and to highlight recent applications in the field of natural product synthesis. The aim is to alert not only the peroxide specialist, but also the synthetic chemist in general, since the first-formed peroxidic products can be used as relay intermediates in the synthesis of nonperoxidic compounds. Autoxidation of HydrocarbonsThe oxidation of hydrocarbons and other organic molecules with oxygen or air is usually referred to as autoxidation [4, 7a, 91. This entirely atom-economical process (Eq. 1, Scheme 1) is ca. 18-24 kcal/mol exothermic and irreversible at temperatures below 250°C. Although the initiation step (Eq. 2) is not well understood [2, lo], it is clear that a chain radical process is involved, with addition of molecular oxygen to R as the initial propagation step (Eq. 3 ) . At oxygen pressures above 100 mm Hg, the reaction of R' with 0 2 proceeds with rate constants approaching the diffusioncontrol limit [7a, 9a]. The second propagation step involves hydrogen atom abstrac- Radicals in Organic Synthesis Edited

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