L-Rhamnulose-1-phosphate and L-fuculose-1-phosphate aldolase mediated multi-enzyme cascade systems for nitrocyclitol synthesis
One-pot multistep stereoselective cascade reactions were implemented for the straightforward synthe-sis of various nitrocyclitols. Two kinases, an aldolase and a phosphatase were involved in this process,together with a spontaneous intramolecular Henry reaction to provide the nitrocyclitol moiety. T...
| Autores: | , , , , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2015 |
| País: | España |
| Institución: | Consejo Superior de Investigaciones Científicas (CSIC) |
| Repositorio: | DIGITAL.CSIC. Repositorio Institucional del CSIC |
| OAI Identifier: | oai:digital.csic.es:10261/113487 |
| Acceso en línea: | http://hdl.handle.net/10261/113487 |
| Access Level: | acceso abierto |
| Palabra clave: | Nitrocyclitol Aldolase Biocatalysis Henry reaction Cascade processes |
| Sumario: | One-pot multistep stereoselective cascade reactions were implemented for the straightforward synthe-sis of various nitrocyclitols. Two kinases, an aldolase and a phosphatase were involved in this process,together with a spontaneous intramolecular Henry reaction to provide the nitrocyclitol moiety. The C Cbond formation catalysed by the aldolase and the nitroaldol reactions were key steps to build the carbocy-cle stereoselectively. The aldolase acceptor substrates were all 4-nitrobutanal structurally based, eitherhydroxylated or unsubstituted at the C2 and/or C3 positions. l-Fuculose-1-phosphate aldolase (FucA)catalysed the formation of the expected (R,R)- or d-erythro aldol, except in the case of 4-nitrobutanal,from which the epimeric (R,S)- or l-threo aldol was also formed. l-Rhamnulose-1-phosphate aldolase con-sistently formed the expected (R,S)- or l-threo aldol together with a minor amount of (R,R)- or d-erythroaldol. The intramolecular Henry reaction was also found to be stereoselective, occurring spontaneouslyonce the aldol was formed due to the presence of both ketone and a terminally positioned nitro group.The combination of this set of reactions successfully furnished 11 nitrocyclitols which have not beendescribed previously in the literature. |
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