Umpolung in reactions catalyzed by thiamine pyrophosphate dependent enzymes
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Subject
dehydrogenase
decarboxylase
thiamine pyro-phosphate
transketolase
umpolung
deshidrogenasa
descarboxilasa
pirofosfato de tiamina
ranscetolasa
umpolung
decarboxylase
thiamine pyro-phosphate
transketolase
umpolung
deshidrogenasa
descarboxilasa
pirofosfato de tiamina
ranscetolasa
umpolung
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Volume Title
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Instituto Tecnológico de Santo Domingo (INTEC)
El intercambio temporal del carácter electrofílico/nucleofí-lico de un átomo mediante manipulación química, es cono-cido con el vocablo alemán de umpolung. Esta inversión de polaridad permite explorar nuevas posibilidades sintéticas que no pueden llevarse a cabo partiendo de la reactividad normal de los grupos funcionales. Se trata de una herra-mienta sintética útil, que también es utilizada por ciertas enzimas en determinadas reacciones bioquímicas que tienen lugar en las células. Las enzimas dependientes del pirofosfato de tiamina, como la piruvato descarboxilasa, la piruvato deshidrogenasa, la α-cetoglutarato deshidrogenasa, la deshidrogenasa de α-cetoácidos de cadena ramificada y la transcetolasa, proporcionan ejemplos claros de umpolungen reacciones celulares. En esta revisión, tras una discusión sobre el significado del término umpolung encontrado en la literatura química, se analizan los mecanismos de reacción y el significado bioquímico de las transformaciones llevadas a cabo por las enzimas mencionadas.
The temporal exchange of the electrophilic/nucleophilic character of an atom by chemical manipulation is known in organic chemistry as umpolung. This inversion of polarity allows the exploration of new synthetic possibilities which cannot be achieved from the normal reactivity of functional groups. It is not only a useful synthetic tool, but it is also utilized by certain enzymes during biochemical reactions in living organisms. Thiamine pyrophosphate dependent enzymes, such as pyruvate decarboxylase, pyruvate dehy-drogenase, α-ketoglutarate dehydrogenase, branched-chain α-keto acids dehydrogenase and transketolase, provide clear examples of umpolung in cellular reactions that fulfill dif-ferent purposes. In this review, after a discussion regarding the meaning of the term umpolung found in the chemical literature, the reaction mechanisms and the biochemical meaning of transformations carried out by the aforemen-tioned enzymes are analyzed.
The temporal exchange of the electrophilic/nucleophilic character of an atom by chemical manipulation is known in organic chemistry as umpolung. This inversion of polarity allows the exploration of new synthetic possibilities which cannot be achieved from the normal reactivity of functional groups. It is not only a useful synthetic tool, but it is also utilized by certain enzymes during biochemical reactions in living organisms. Thiamine pyrophosphate dependent enzymes, such as pyruvate decarboxylase, pyruvate dehy-drogenase, α-ketoglutarate dehydrogenase, branched-chain α-keto acids dehydrogenase and transketolase, provide clear examples of umpolung in cellular reactions that fulfill dif-ferent purposes. In this review, after a discussion regarding the meaning of the term umpolung found in the chemical literature, the reaction mechanisms and the biochemical meaning of transformations carried out by the aforemen-tioned enzymes are analyzed.
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info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
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info:eu-repo/semantics/publishedVersion
Artículos
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Science, Environment and Climate; Vol. 2 No. 2 (2019): Science, Environment and Climate; 27-42
Ciencia, Ambiente y Clima; Vol. 2 Núm. 2 (2019): Ciencia, Ambiente y Clima; 27-42
2636-2333
2636-2317
10.22206/cac.2019.v2i2
Ciencia, Ambiente y Clima; Vol. 2 Núm. 2 (2019): Ciencia, Ambiente y Clima; 27-42
2636-2333
2636-2317
10.22206/cac.2019.v2i2