Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 80, Issue 8, Pages 3745-3751Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.5b00515
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Funding
- Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP) [2005/58320-4, 2012/13807-7, 2012/02428-5, 2014/14866-2, 2014/22136-4]
- Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq) [304094/2013-7]
- Coordenadoria de Aperfeicoamento de Pessoal de Ensino Superior (CAPES)
- Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP) [12/13807-7] Funding Source: FAPESP
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The chemiluminescent decomposition of 1,2-dioxetanones (alpha-peroxylactones), catalyzed by an appropriate fluorescent activator, is an important simple model for efficient bioluminescent transformations. In this work, we report experimental data on the catalyzed decomposition of two spiro-substituted 1,2-dioxetanone derivatives, which support the occurrence of an intermolecular electron transfer from the activator to the peroxide. The low efficiency of the studied systems is associated with steric hindrance during the chemiexcitation sequence, rationalized using the concept of supermolecule formation between the peroxide and the catalyst. This approach explains the difference in the chemiexcitation efficiencies in the decomposition of four-membered cyclic peroxide derivatives: 1,2-dioxetanes, 1,2-dioxetanones, and 1,2-dioxetanedione (the intermediate in the peroxyoxalate reaction), which are the most important model compounds for excited-state formation in chemiluminescence and bioluminescence processes.
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