Lipase catalysed kinetic resolution of racemic 1,2-diols containing a chiral quaternary center

Optically active 1,2-diols are valuable buildings blocks in organic synthesis. In the present paper, a set of racemic 1,2-diols with an ester functional group are prepared, starting from -ketoesters in a three-step procedure with moderate yields. The racemic 1,2-diols, containing a chiral quaternary center in their structure, are subjected to selective acylation in order to perform their kinetic resolution catalysed by a set of commercially available lipases. Under optimized reaction conditions, good conversions and enantioselectivities are achieved by using the lipase PSL-C from Pseudomonas cepacia in tert-butyl methyl ether. This biocatalyst could be reused up to five times without losing its properties.Ministerio de Economía y Competitividad (contract RYC-2012-10014 for G.d.G., Grants CTQ2016-76908-C2-1-P and CTQ2016-76908-C2-2-P)European FEDER FundsJunta de Andalucía (Grant 2012/FQM 10787

Correction: de Gonzalo, G. Lipase Catalysed Kinetic Resolution of Racemic 1,2-Diols Containing a Chiral Quaternary Center. Molecules 2018, 23, 1585

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Biocatalysis as Useful Tool in Asymmetric Synthesis: An Assessment of Recently Granted Patents (2014–2019)

The broad interdisciplinary nature of biocatalysis fosters innovation, as different technical fields are interconnected and synergized. A way to depict that innovation is by conducting a survey on patent activities. This paper analyses the intellectual property activities of the last five years (2014–2019) with a specific focus on biocatalysis applied to asymmetric synthesis. Furthermore, to reflect the inventive and innovative steps, only patents that were granted during that period are considered. Patent searches using several keywords (e.g., enzyme names) have been conducted by using several patent engine servers (e.g., Espacenet, SciFinder, Google Patents), with focus on granted patents during the period 2014–2019. Around 200 granted patents have been identified, covering all enzyme types. The inventive pattern focuses on the protection of novel protein sequences, as well as on new substrates. In some other cases, combined processes, multi-step enzymatic reactions, as well as process conditions are the innovative basis. Both industries and academic groups are active in patenting. As a conclusion of this survey, we can assert that biocatalysis is increasingly recognized as a useful tool for asymmetric synthesis and being considered as an innovative option to build IP and protect synthetic routes

Biocatalyzed redox processes employing green reaction media

The application of biocatalysts to perform reductive/oxidative chemical processes has attracted great interest in recent years, due to their environmentally friendly conditions combined with high selectivities. In some circumstances, the aqueous buffer medium normally employed in biocatalytic procedures is not the best option to develop these processes, due to solubility and/or inhibition issues, requiring biocatalyzed redox procedures to circumvent these drawbacks, by developing novel green non-conventional media, including the use of biobased solvents, reactions conducted in neat conditions and the application of neoteric solvents such as deep eutectic solvents

Recent developments in the synthesis of β-diketones

Apart from being one of the most important intermediates in chemical synthesis, broadly used in the formation of C–C bonds among other processes, the β-dicarbonyl structure is present in a huge number of biologically and pharmaceutically active compounds. In fact, mainly derived from the well-known antioxidant capability associated with the corresponding enol tautomer, β-diketones are valuable compounds in the treatment of many pathological disorders, such as cardiovascular and liver diseases, hypertension, obesity, diabetes, neurological disorders, inflammation, skin dis-eases, fibrosis, or arthritis; therefore, the synthesis of these structures is an area of overwhelming interest for organic chemists. This paper is devoted to the advances achieved in the last ten years for the preparation of 1,3-diketones, using different chemical (Claisen, hydration of alkynones, decar-boxylative coupling) or catalytic (biocatalysis, organocatalytic, metal-based catalysis) methodologies: Additionally, the preparation of branched β-dicarbonyl compounds by means of α-functionalization of non-substituted 1,3-diketones are also discussed

Recent trends in synthetic enzymatic cascades promoted by alcohol dehydrogenases

Alcohol dehydrogenases have fascinated chemists over the span of a few decades to catalyze oxidation and reduction reactions and have been increasingly incorporated as bio- catalysts in scaled-up industrial processes for the production of valuable chiral compounds under mild and environmentally friendly conditions. In this review, we discuss recent advances on alcohol dehydrogenases coupled in cascade reactions with other enzyme classes, chemocatalysts, or organocatalysts to obtain high value–added products. The examples include deracemization processes for the synthesis of chiral diols and amino alcohols, whole-cell and co-expression systems, and chemoenzymatic and organoenzymatic cascades, with a vision for future developments

Multienzymatic processes involving baeyer–villiger monooxygenases

Baeyer–Villiger monooxygenases (BVMOs) are flavin-dependent oxidative enzymes capable of catalyzing the insertion of an oxygen atom between a carbonylic Csp2 and the Csp3 at the alpha position, therefore transforming linear and cyclic ketones into esters and lactones. These enzymes are dependent on nicotinamides (NAD(P)H) for the flavin reduction and subsequent reaction with molecular oxygen. BVMOs can be included in cascade reactions, coupled to other redox enzymes, such as alcohol dehydrogenases (ADHs) or ene-reductases (EREDs), so that the direct conversion of alcohols or α,β-unsaturated carbonylic compounds to the corresponding esters can be achieved. In the present review, the different synthetic methodologies that have been performed by employing multienzymatic strategies with BVMOs combining whole cells or isolated enzymes, through sequential or parallel methods, are described, with the aim of highlighting the advantages of performing multienzymatic systems, and show the recent advances for overcoming the drawbacks of using BVMOs in these techniques.Ministerio de Ciencia e Innovación PID2019-105337RB-C22Banco Santander-UCM PR87/19-2267

P450BM3-Catalyzed Oxidations Employing Dual Functional Small Molecules

A set of dual functional small molecules (DFSMs) containing different amino acids has been synthesized and employed together with three different variants of the cytochrome P450 monooxygenase P450BM3 from Bacillus megaterium in H2O2-dependent oxidation reactions. These DFSMs enhance P450BM3 activity with hydrogen peroxide as an oxidant, converting these enzymes into formal peroxygenases. This system has been employed for the catalytic epoxidation of styrene and in the sulfoxidation of thioanisole. Various P450BM3 variants have been evaluated in terms of activity and selectivity of the peroxygenase reactions.MINECO-CTQ2016-76908-C2-1,2-PComisión Europea de Investigación-ERC-648026Unión Europea-H2020-BBI-PPP-2015-2-1-720297Organización Holandesa de Investigación Científica (VICI)-724.014.00

Indicadores Sintéticos para la Proyección de Imacec en Chile

This paper studies the informational content of synthetic indicators of economic activity for projecting the monthly index of economic activity (Imacec) for Chile. Comparing them to the Urrutia-Sánchez (2008) model, which employs energy production, and calendar and seasonal components to forecast the Imacec, models employing synthetic leading indicators and financial conditions indicators are competitive in terms of the MSFE. Moreover, we show that combinations of different forecasting strategies with small bias present improvements in terms of the MSFE with respect to individual models. We also show that, due to their inertial behavior, projections with synthetic indicators display errors that last for many periods after an exogenous event (such as an earthquake). Specifications with variables that quickly adjust to economic activity, such as energy consumption, do not have this problem.

Positive impact of natural deep eutectic solvents on the biocatalytic performance of 5-hydroxymethyl-furfural oxidase

Deep eutectic solvents (DESs) have been applied as cosolvents in various biocatalytic processes during recent years. However, their use in combination with redox enzymes has been limited. In this study, we have explored the beneficial effects of several DES as cosolvents on the performance of 5-hydroxymethylfurfural oxidase (HMFO), a valuable oxidative enzyme for the preparation of furan-2,5-dicarboxylic acid (FDCA), and other compounds, such as carbonyl compounds and carboxylic acids. The use of natural DESs, based on glucose and fructose, was found to have a positive effect. Higher conversions are obtained for the synthesis of several oxidized compounds, including FDCA. Depending on the type of DES, the stability of HMFO could be significantly improved. As the use of DES increases the solubility of many substrates while they only mildly affect dioxygen solubility, this study demonstrates that biocatalysis based on HMFO and other redox biocatalysts can benefit from a carefully selected DES