Coupling biocatalysis and click chemistry: one-pot two-step convergent synthesis of enantioenriched 1,2,3-triazole-derived diols

A fully convergent one-pot two-step synthesis of different chiral 1,2,3-triazole-derived diols in high yields and excellent enantio- and diastereoselectivities has been achieved under very mild conditions in aqueous medium by combining a single alcohol dehydrogenase (ADH) with a Cu-catalysed ‘click’ reaction.Fil: Cuetos, Aníbal. Universidad de Oviedo; EspañaFil: Bisogno, Fabricio Román. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. Universidad de Oviedo; EspañaFil: Lavandera, Iván. Universidad de Oviedo; EspañaFil: Gotor, Vicente. Universidad de Oviedo; Españ

Access to Enantiopure alpha-Alkyl-beta-hydroxy Esters through Dynamic Kinetic Resolutions Employing Purified/Overexpressed Alcohol Dehydrogenases

α-Alkyl-β-hydroxy esters were obtained via dynamic kinetic resolution (DKR) employing purified or crude E. coli overexpressed alcohol dehydrogenases (ADHs). ADH-A from R. ruber, CPADH from C. parapsilosis and TesADH from T. ethanolicus afforded syn-(2R,3S) derivatives with very high selectivities for sterically not impeded ketones ('small-bulky' substrates), while ADHs from S. yanoikuyae (SyADH) and Ralstonia sp. (RasADH) could also accept bulkier keto esters ('bulky-bulky' substrates). SyADH also provided preferentially syn-(2R,3S) isomers and RasADH showed in some cases good selectivity towards the formation of anti-(2S,3S) derivatives. With anti-Prelog ADHs such as LBADH from L. brevis or LKADH from L. kefir, syn-(2S,3R) alcohols were obtained with high conversions and diastereomeric excess in some cases, especially with LBADH. Furthermore, due to the thermodynamically favoured reduction of these substrates, it was possible to employ just a minimal excess of 2-propanol to obtain the final products with quantitative conversions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.Fil: Cuetos, Aníbal. Universidad de Oviedo; EspañaFil: Rioz Martínez, Ana. Universidad de Oviedo; EspañaFil: Bisogno, Fabricio Román. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Oviedo; EspañaFil: Grischek, Barbara. University of Graz; AustriaFil: Lavandera, Iván. Universidad de Oviedo; EspañaFil: De Gonzalo, Gonzalo. Universidad de Oviedo; EspañaFil: Kroutil, Wolfgang. University of Graz; AustriaFil: Gotor, Vicente. Universidad de Oviedo; Españ