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Oxidising agent and catalyst chirality effect on epoxidation of R-(+)- Limonene using Jacobsen-type catalysts
Efecto del agente oxidante y la quiralidad del catalizador en la epoxidación de R-(+)-limoneno con catalizadores tipo Jacobsen
DOI:
https://doi.org/10.15446/ing.investig.v28n2.14890Keywords:
diastereoselectivity, epoxidation, R-( )-Limonene, oxidising agent type, asymmetric induction, chiral, achiral (en)diastereoselectividad, epoxidación, R-( )-Limoneno, agente oxidante, inducción asimétrica, catalizador quiral, catalizador aquiral (es)
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The oxidising agent effect on R-(+)-Limonene epoxide diastereoselectivity using chiral and achiral Jacobsen’s type catalysts is presented. The type of oxidising agent strongly influences diastereoselectivity. Moderate diastereomeric excesses were achieved in the presence of oxidising agents prepared in situ but in the absence of catalyst (23% for DMD and 29% for O2/pivalaldehyde). Similar diastereomeric excesses were obtained with both chiral and achiral catalyst when the oxidising agents were prepared in situ; 56% and 50% excesses were obtained when using DMD for the chiral and achiral catalyst (respectively) and 38% using O2/pivalaldehyde for both catalysts. Diastereomeric excesses were not observed in the absence of catalyst when using commercial oxidising agents; the chiral catalyst presented larger diastereomeric excesses than its achiral counterpart: 65% and 38% excess using NaOCl for the chiral and achiral catalyst, respectively, and 79% and 39% using m-CPBA for the chiral and achiral catalyst, respectively. This suggests that at least one oxidant species, different from the conventionally accepted (MnV(oxo)), might be involved in this catalytic process. A modification of the traditional catalytic cycle is proposed considering the type of oxidising agent. The catalyst’s chiral centre appears to govern asymmetric induction when commercial oxidising agents are used, whereas the R-(+)-Limonene chiral centre appears to govern asymmetric induction in the presence of
in situ-prepared oxidising agents. On the other hand, the chemical stability of Jacobsen’s catalyst improved when in situ produced DMD was used as oxidising agent.
Se presenta el efecto del agente oxidante en la diastereoselectividad del epóxido de R-(+)-limoneno utilizando catalizadores tipo Jacobsen, tanto en su forma quiral como aquiral. Se encontró que el tipo de agente oxidante afecta marcadamente la diastereoselectividad. Así, en presencia de agentes oxidantes preparados in situ se obtuvieron excesos diastereoméricos moderados y similares en ausencia de catalizador (23% con DMD y 29% con O2/ pivalaldehído). También se observó este comportamiento en presencia de ambos catalizadores. Con DMD se obtuvo 56% con el catalizador quiral y 50% con el aquiral, y con O2/pivalaldehído se obtuvo 38% con ambos catalizadores. Por otro lado, con los agentes oxidantes comerciales no se presentó exceso diastereomérico en ausencia de catalizador. En este caso, el catalizador quiral alcanzó un exceso diastereomérico mayor que el aquiral. Con NaOCl se logró 65% con el catalizador quiral y 38% con el aquiral, y con m-CPBA 79% con el catalizador quiral y 39% con el aquiral. Lo anterior sugiere que debe existir al menos otra especie oxidante intermediaria diferente a la aceptada convencionalmente (MnV(oxo)). De esta manera, se propone una modificación al ciclo catalítico tradicional teniendo en cuenta el agente oxidante. En presencia de los agentes oxidantes comerciales se presume que el centro quiral del catalizador gobierna la inducción asimétrica, mientras que para los agentes oxidantes preparados in situ la inducción asimétrica estaría gobernada por el centro quiral del R- (+)-limoneno. Adicionalmente se encontró que la estabilidad química del catalizador de Jacobsen mejoró cuando el agente oxidante fue DMD generado in situ.
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Copyright (c) 2008 Juliana Reyes Calle, Jairo Antonio Cubillos Lobo, Consuelo Montes de Correa, Aída Luz Villa Holguín de P.
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