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L ‐Rhamnulose‐1‐phosphate Aldolase from Thermotoga maritima in Organic Synthesis: One‐Pot Multistep Reactions for the Preparation of Imino‐ and Nitrocyclitols
Author(s) -
OrozGuinea Isabel,
Hernández Karel,
Camps Bres Flora,
GuérardHélaine Christine,
Lemaire Marielle,
Clapés Pere,
GarcíaJunceda Eduardo
Publication year - 2015
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201500187
Subject(s) - thermotoga maritima , diastereomer , chemistry , aldol reaction , aldolase a , stereoselectivity , aldehyde , organic synthesis , stereochemistry , enantioselective synthesis , enzyme catalysis , enzyme , catalysis , organic chemistry , escherichia coli , biochemistry , gene
Rhamnulose‐1‐phosphate aldolase from Thermotoga maritima (Rhu1PA Tm ) has been recently cloned and characterised. This hyperthermophilic enzyme offers intriguing possibilities for practical catalysis. This is due to its high stability under extreme reaction conditions, such as high temperature or the presence of organic co‐solvents. The Rhu1PA Tm potentiality in organic synthesis has been explored focusing on (i) the reaction stereocontrol, (ii) the possibility of combining it with other mesophilic enzymes in multienzyme systems and (iii) its application to the synthesis of imino‐ and nitrocyclitols. In our study, the diastereoselectivity of Rhu1PA Tm was similar to the one reported for Rhu1PA from Escherichia coli (Rhu1PA Ec ). However, we observed significant differences for some aldehyde acceptors. Indeed, the diastereoselectivity control was not complete, since mixtures of L ‐ threo (2 R ,3 S ; natural stereopreference) and D ‐ erythro (2 R ,3 R ) diastereoisomers were obtained as described for Rhu1PA Ec . Rhu1PA Tm was able to catalyse aldol reactions using nitroaldehydes and N ‐Cbz‐aminoaldehydes. Conversion of the selected nitroaldehydes was complete, leading to mixtures of L ‐ threo and D ‐erythro diastereoisomers, in 95:5 and 75:25 ratios. When N ‐Cbz‐aminoaldehydes were used, aldol reaction yields were lower and the stereoselectivity L ‐ threo : D ‐erythro ranged between 32:68 to>95:5.