Article
Chemistry, Organic
Laura Suarez-Escobedo, Vicente Gotor-Fernandez
Summary: In this study, the esterification of cinnamic acid using ethanol as the nucleophile and CAL-B as the biocatalyst was deeply investigated. The role of solvent in the production of ethyl cinnamate was emphasized, with hexane selected as the optimal solvent. Key parameters affecting enzyme efficiency were identified, and a series of ethyl esters with different substitutions on the aromatic ring were successfully produced using lipase-catalyzed esterification.
Article
Chemistry, Physical
Martin Soto, Vicente Gotor-Fernandez, Humberto Rodriguez-Solla, Walter Baratta
Summary: The transfer hydrogenation of flavanones and ortho-hydroxychalcones catalyzed by ruthenium pincer complexes allows the synthesis of ortho-hydroxy 1,3-diarypropanols with high yield and selectivity. The amount of co-catalyst is crucial for the reduction reaction, while using pincer catalysts with specific ligands can achieve high enantiomeric excess and moderate conversion rates in the reduction of flavanones.
Article
Chemistry, Multidisciplinary
Sergio Gonzalez-Granda, Ivan Lavandera, Vicente Gotor-Fernandez
Summary: The combination of gold(I) and enzyme catalysis in a two-step approach was used to synthesize optically pure beta,beta-disubstituted allylic alcohols. The cascade reaction involves a gold N-heterocyclic carbene and an enzyme in aqueous medium under mild conditions, leading to good yields of optically active compounds. This method was extended to various derivatives and the use of alcohol dehydrogenases with opposite selectivity allowed for the production of enantiomers of allyl alcohol.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Sergio Gonzalez-Granda, Lorena Escot, Ivan Lavandera, Vicente Gotor-Fernandez
Summary: A concurrent cascade reaction using a gold(I) N-heterocyclic carbene and an alcohol dehydrogenase was developed for the synthesis of enantiopure halohydrins. The reaction proceeds through regioselective hydration of haloalkynes followed by stereoselective bioreduction of alpha-halomethyl ketone intermediates. The method demonstrates high selectivity and good yields of chloro- and bromohydrins. Additionally, the synthesis of enantiomers of styrene oxide in high yields and optical purities was achieved.
Article
Chemistry, Applied
Sergio Gonzalez-Granda, Nikolaos Tzouras, Steven P. Nolan, Ivan Lavandera, Vicente Gotor-Fernandez
Summary: The compatibility between gold(I) catalysts and amine transaminases has been explored for the selective synthesis of enantioenrich ed allylic amines from racemic propargylic alcohols. The use of a cascade process involving a gold(I)-catalyzed rearrangement and an enzyme-catalyzed transamination led to the successful synthesis of the desired amines. The results showed that the N-heterocyclic carbene complex used as the catalyst, combined with selective amine transaminases, allowed for the asymmetric synthesis of enantioenrich ed allylic amines.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Jorge Gonzalez-Rodriguez, Jesus Albarran-Velo, Raquel G. Soengas, Ivan Lavandera, Vicente Gotor-Fernandez, Humberto Rodriguez-Solla
Summary: In this study, a bienzymatic cascade was developed and optimized to efficiently synthesize enantiopure chlorohydrins. The reaction showed high conversion and selectivity under mild conditions.
Review
Chemistry, Multidisciplinary
Sergio Gonzalez-Granda, Jesus Albarran-Velo, Ivan Lavandera, Vicente Gotor-Fernandez
Summary: The combination of metal-, photo-, enzyme-, and/or organocatalysis is a versatile approach in synthetic chemistry, particularly for the creation of chiral centers. This review focuses on the recent developments in the simultaneous use of enzymes and transition metal catalysts, as well as the integration of multiple bioprocesses and metal-catalyzed transformations in linear cascades. Challenges such as catalyst compatibility, reaction media, and cross-reactivities are addressed by strategies such as catalyst coimmobilization, compartmentalization, and flow chemistry. The review also highlights the application of bionanohybrid materials, where enzymes and metals are coimmobilized on suitable supports.
Article
Chemistry, Applied
Laura Rodriguez-Fernandez, Jesus Albarran-Velo, Ivan Lavandera, Vicente Gotor-Fernandez
Summary: The photocatalytic Meerwein arylation between aromatic diazonium salts and isopropenyl acetate in aqueous medium was studied under blue LED light irradiation. Optimization of reaction conditions allowed the synthesis of various 1-arylpropan-2-ones with up to 95% yield using [Acr-Mes]ClO4 as the photocatalyst. Furthermore, a one-pot sequential photobiocatalytic approach combining the Meerwein arylation with bioreduction of ketone intermediates was developed, leading to the synthesis of 1-arylpropan-2-ol enantiomers with up to 76% overall yield and high stereoselectivity.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Applied
Sergio Gonzalez-Granda, Georg Steinkellner, Karl Gruber, Ivan Lavandera, Vicente Gotor-Fernandez
Summary: The combination of gold(I) and enzyme catalysis allows for the selective synthesis of a series of nor(pseudo)ephedrine derivatives. This approach involves the hydration of 1-phenylprop-2-yn-1-yl acetate or N-(1-phenylprop-2-yn-1-yl)acetamide using IPrAuNTf2 catalyst, followed by (dynamic) asymmetric biotransamination or bioreduction of the resulting keto ester or keto amide intermediates. Enzyme actions exhibit high stereoselectivity towards methyl ketones, enabling the synthesis of enantio- and diastereomerically enriched products. The use of propargyl esters or amides as starting materials allows for the production of amino alcohol, diol, and diamine derivatives with good yields and high (stereo)selectivity.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Chemistry, Multidisciplinary
Sergio Gonzalez-Granda, Lorena Escot, Ivan Lavandera, Vicente Gotor-Fernandez
Summary: The combination of metal and enzyme catalysis has attracted great attention in organic synthesis due to its ability to achieve diverse organic molecules with the stereospecificity displayed by enzymes. This minireview focuses on the action of metal species (Pd, Ru, Au, Ir, Fe, etc.) in combination with different enzymes, highlighting the design of sequential processes and concurrent cascades to overcome incompatibilities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Nicoletta Cascelli, Vincenzo Lettera, Giovanni Sannia, Vicente Gotor-Fernandez, Ivan Lavandera
Summary: Laccases are shown to be valuable in biocatalysis for the green and selective oxidation of furfuryl alcohol into furfural using mediators. Various parameters including pH, enzyme/mediator composition, buffer type, cosolvent tolerance, and reaction times are investigated. Under optimal conditions, quantitative production of furfural is achieved after 16 h using 20 mol % of TEMPO as mediator and 5.8 U mL(-1) of POXC and POXA1b laccases from Pleurotus ostreatus. POXC exhibits remarkable catalytic ability at pH 6.5, while POXA1b is notable for its high stability. Furfural conversions of up to 95% are obtained after 72 h using only 5 mol % of TEMPO at 100 mM. Furthermore, furfuryl alcohol bioamination is successfully achieved through a one-pot sequential approach using amine transaminase from Chromobacterium violaceum, providing furfuryl amine, a key compound for the polymer industry.
Article
Biochemistry & Molecular Biology
Antia Pintor, Nicoletta Cascelli, Alexey Volkov, Vicente Gotor-Fernandez, Ivan Lavandera
Summary: This study discloses the biocatalytic amination of furan-based compounds using amine transaminases (ATAs) and isopropylamine (IPA) as amine donors. Optimal biocatalysts were identified and high levels of product formation were achieved. pH was found as a key factor affecting the transformation.
Article
Chemistry, Multidisciplinary
Antia Pintor, Ivan Lavandera, Alexey Volkov, Vicente Gotor-Fernandez
Summary: The study focused on finding an ideal biocatalyst for the acylation of furfurylamine and 5-hydroxymethylfurfurylamine (HMFA), and identified immobilized Candida antarctica lipase B (CALB) as a suitable option. CALB was immobilized on different supports and the use of a polymer-coated controlled porosity glass carrier material yielded an active and stable enzymatic preparation for the acylation reaction. By controlling the amount of acyl donor in the reaction, selective modification of the amine group of HMFA was achieved, resulting in the formation of hydroxy amides. The reaction conditions and substrate concentration were optimized to achieve high conversions and yields. The study also demonstrated the possibility of obtaining orthogonally protected HMFA-derived amido esters through a one-pot process.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Antia Pintor, Ashley P. Mattey, Ivan Lavandera, Vicente Gotor-Fernandez, Alexey Volkov
Summary: The use of multienzymatic systems has become popular for complex (asymmetric) syntheses. Incompatible substrates, reagents, and enzymes can limit the applicability of a cascade reaction in batch conditions, so flow systems are preferred. Immobilized enzymes in continuous flow reactors enable the segregation and isolation of enzymes, allowing for otherwise challenging reaction cascades.
Article
Biochemistry & Molecular Biology
Nicoletta Cascelli, Vicente Gotor-Fernandez, Ivan Lavandera, Giovanni Sannia, Vincenzo Lettera
Summary: Modern biocatalysis relies on fast and efficient screening methods to find novel biocatalysts for chemical production. This study introduces a colorimetric assay using Schiff-based polymers to detect the presence of DFF in reaction mixtures.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
