The synthesis of chiral N-heterocyclic carbene–borane and –diorganoborane complexes and their use in the asymmetric reduction of ketones

Chiral N-heterocyclic carbene–borane complexes have been synthesised, and have been shown to reduce ketones with Lewis acid promotion. Chiral N-heterocyclic carbene–borane and –diorganoborane complexes can reduce ketones with enantioselectivities up to 75% and 85% ee, respectively.

Biotransformations of Substituted Phenylethanols and Acetophenones by Environmental Bacteria

Whole cells of hydrocarbon-degrading bacteria, isolated from polluted sediments in the Santos Estuary (Baixada Santista, Sao Paulo, Brazil), were able to catalyse oxidoreduction reactions with various substituted phenylethanols and acetophenones as substrates. A number of substituted phenylethanols were formed with high (>99 %) enantiomeric excess. The results of microbial oxidation of phenylethanols 2, 3, 5-7 by Acinetobacter sp. 6.4T and the reduction of acetophenones 1a-6a by Serratia marcescens 5.4T showed that the bacteria used as biocatalysts in this study present significant potential for exploitation in biotechnological processes. The reduction of prochiral acetophenones by Serratia marcescens 3.5T yielded optically active alcohols with 90-99 % enantiomeric excess, and Acinetobacter sp. 6.4T is a potential biocatalyst for the oxidation of alcohols.

Bioreduction of Acetophenone Derivatives by Red Marine Algae Bostrychia radicans and B. tenella, and Marine Bacteria Associated

The biocatalytic reduction of acetophenone derivatives was exploited by using algal biomass from Bostrychia radicans and B. tenella producing exclusively (S)-2-phenylethanols with high enantiomeric excess (> 99% ee). Bacterial populations associated with algal biomass were identified as the Bacillus genus. This report deals with the first investigations involving the use of marine bacteria associated with B. radicans and B. tenella marine algae for the biocatalytic reduction of acetophenone derivatives.

Bioreduction of beta-carboline imines to amines employing Saccharomyces bayanus

beta-Carboline imine reductions mediated by Saccharomyces bayanus have been described achieving moderate to good enantiomeric excesses of the amine products. The enantiomeric excesses of the bioreduction showed a dependence on the imine substituents. Compounds presenting C(1)-C(11) aliphatic substituent groups afforded amines with an (S)-configuration, whereas C(15) and higher aliphatic, and aromatic substituted B-carboline imines achieved inversion of the configuration in the final (R)-2 amine products. Based on this data, a model for the Saccharomyces reduction is proposed. (C) 2010 Elsevier Ltd. All rights reserved.

Álcoois quirais: métodos químicos e catalíticos de obtenção por redução assimétrica

The importance of chiral alcohols as starting materials for the production of fine chemicals and as useful chirons for the building of several interesting molecules or natural products is reported. The useful and common methods of asymmetric reduction such as the chemical (with organoboron or organoaluminum reagents) and the catalytic ones (with ruthenium or rhodium complexes) for preparation of chiral alcohols are described; even the newer and much more rare electrocatalytic methods are reported.

Biotransformation of alpha-Bromoacetophenones by the Marine Fungus Aspergillus sydowii

The biotransformation reactions of alpha-bromoacetophenone (1), p-bromo-alpha-bromoacetophenone (2), and p-nitro-alpha-bromoacetophenone (3) by whole cells of the marine fungus Aspergillus sydowii Ce19 have been investigated. Fungal cells that had been grown in artificial sea water medium containing a high concentration of chloride ions (1.20 M) catalysed the biotransformation of 1 to 2-bromo-1-phenylethanol 4 (56%), together with the alpha-chlorohydrin 7 (9%), 1-phenylethan-1,2-diol 9 (26%), acetophenone 10 (4%) and phenylethanol 11 (5%) identified by GC-MS analysis. In addition, it was observed that the enzymatic reaction was accompanied by the spontaneous debromination of 1 to yield alpha-chloroacetophenone 5 (9%) and alpha-hydroxyacetophenone 6 (18%) identified by GC-FID analysis. When 2 and 3 were employed as substrates, various biotransformation products were detected but the formation of halohydrins was not observed. It is concluded that marine fungus A. sydowii Ce19 presents potential for the biotransformations of bromoacetophenone derivatives.

Kinetic resolution of iodophenylethanols by Candida antarctica lipase and their application for the synthesis of chiral biphenyl compounds

The kinetic resolution of (+/-)-iodophenylethanols was carried out using lipase from Candida antarctica and in some cases the enantiomeric excesses were high (up to >98%). Enantiomerically enriched (S)-iodophenylethanols produced by the enzymatic resolution process were used in the synthesis of chiral biphenyl compounds by the Suzuki reaction with good yields (63-65%). (C) 2010 Elsevier Ltd. All rights reserved.

Bioreduction of alpha-chloroacetophenone by whole cells of marine fungi

The asymmetric reduction of 2-chloro-1-phenylethanone (1) by seven strains of marine fungi was evaluated and afforded (S)-(-)-2-chloro-1-phenylethanol with, in the best case, an enantiomeric excess of 50% and an isolated yield of 60%. The ability of marine fungi to catalyse the reduction was directly dependent on growth in artificial sea water-based medium containing a high concentration of Cl(-) (1.2 M). When fungi were grown in the absence of artificial sea water, no reduction of 1 by whole cells was observed. The biocatalytic reduction of 1 was more efficient at neutral rather than acidic pH values and in the absence of glucose as co-substrate.

Lipase-catalyzed kinetic resolution of beta-borylated carboxylic esters

The kinetic resolution of chiral beta-borylated carboxylic esters via lipase-catalyzed hydrolysis and transesterification reactions was studied. The enantioselective hydrolysis catalyzed by CAL-B furnished the beta-borylated carboxylic acid with reasonable enantiomeric excess (62% ee), while both methyl and ethyl beta-borylated carboxylic esters were recovered with excellent ee (>99%). Meanwhile, the transesterification reaction of beta-borylated carboxylic esters and several alcohols, catalyzed by CAL-B, only indicated a high selectivity when ethanol and methyl-(beta-pinacolylboronate)-butanoate were used as substrates, which gave ethyl-(beta-pinacolylboronate)-butanoate with >99% ee. (C) 2012 Elsevier Ltd. All rights reserved.

Synthesis and organocatalyzed enantioselective transfer-hydrogenation of beta-amino nitroolefins

The importance of the β-amino nitroalkanes is due to their high versatility allowing a straightforward entry to a variety of nitrogen-containing chiral building blocks; furthermore obtaining them in enantiopure form allows their use in the synthesis of biologically active compounds or their utilization as chiral ligands for different uses. In this work, a reaction for obtaining enantiopure β-amino nitroalkanes through asymmetric organocatalysis has been developed. The synthetic strategy adopted for the obtainment of these compounds was based on an asymmetric reduction of β-amino nitroolefins in a transfer hydrogenation reaction, involving an Hantzsch ester as hydrogen source and a chiral thiourea as organic catalyst. After the optimization of the reaction conditions over the β-acyl-amino nitrostyrene, we tested the reaction generality over other aromatic compound and for Boc protected substrate both aromatic and aliphatic. A scale-up of the reaction was also performed.

Full label space reduction in MPLS networks: asymmetric merged tunneling

Traffic Engineering objective is to optimize network resource utilization. Although several works have been published about minimizing network resource utilization in MPLS networks, few of them have been focused in LSR label space reduction. This letter studies Asymmetric Merged Tunneling (AMT) as a new method for reducing the label space in MPLS network. The proposed method may be regarded as a combination of label merging (proposed in the MPLS architecture) and asymmetric tunneling (proposed recently in our previous works). Finally, simulation results are performed by comparing AMT with both ancestors. They show a great improvement in the label space reduction factor

Asymmetric tunnels in P2MP LSPs as a label space reduction method

The objective of traffic engineering is to optimize network resource utilization. Although several works have been published about minimizing network resource utilization, few works have focused on LSR (label switched router) label space. This paper proposes an algorithm that takes advantage of the MPLS label stack features in order to reduce the number of labels used in LSPs. Some tunnelling methods and their MPLS implementation drawbacks are also discussed. The described algorithm sets up NHLFE (next hop label forwarding entry) tables in each LSR, creating asymmetric tunnels when possible. Experimental results show that the described algorithm achieves a great reduction factor in the label space. The presented works apply for both types of connections: P2MP (point-to-multipoint) and P2P (point-to-point)

A Label space reduction algorithm for P2MP LSPs using asymmetric tunnels

The aim of traffic engineering is to optimise network resource utilization. Although several works on minimizing network resource utilization have been published, few works have focused on LSR label space. This paper proposes an algorithm that uses MPLS label stack features in order to reduce the number of labels used in LSPs forwarding. Some tunnelling methods and their MPLS implementation drawbacks are also discussed. The algorithm described sets up the NHLFE tables in each LSR, creating asymmetric tunnels when possible. Experimental results show that the algorithm achieves a large reduction factor in the label space. The work presented here applies for both types of connections: P2MP and P2P

Asymmetric tunnels in P2MP LSPs as a label space reduction method

The objective of traffic engineering is to optimize network resource utilization. Although several works have been published about minimizing network resource utilization, few works have focused on LSR (label switched router) label space. This paper proposes an algorithm that takes advantage of the MPLS label stack features in order to reduce the number of labels used in LSPs. Some tunnelling methods and their MPLS implementation drawbacks are also discussed. The described algorithm sets up NHLFE (next hop label forwarding entry) tables in each LSR, creating asymmetric tunnels when possible. Experimental results show that the described algorithm achieves a great reduction factor in the label space. The presented works apply for both types of connections: P2MP (point-to-multipoint) and P2P (point-to-point)

A Label space reduction algorithm for P2MP LSPs using asymmetric tunnels

The aim of traffic engineering is to optimise network resource utilization. Although several works on minimizing network resource utilization have been published, few works have focused on LSR label space. This paper proposes an algorithm that uses MPLS label stack features in order to reduce the number of labels used in LSPs forwarding. Some tunnelling methods and their MPLS implementation drawbacks are also discussed. The algorithm described sets up the NHLFE tables in each LSR, creating asymmetric tunnels when possible. Experimental results show that the algorithm achieves a large reduction factor in the label space. The work presented here applies for both types of connections: P2MP and P2P