Cyanobacterial biorefinery: Towards economic feasibility through the maximum valorization of biomass.

Cyanobacteria are well known for their plethora of applications in the fields of food industry, pharmaceuticals and bioenergy. Their simple growth requirements, remarkable growth rate and the ability to produce a wide range of bio-active compounds enable them to act as an efficient biorefinery for the production of valuable metabolites. Most of the cyanobacteria based biorefineries are targeting single products and thus fails to meet the efficient valorization of biomass. On the other hand, multiple products recovering cyanobacterial biorefineries can efficiently valorize the biomass with minimum to zero waste generation. But there are plenty of bottlenecks and challenges allied with cyanobacterial biorefineries. Most of them are being associated with the production processes and downstream strategies, which are difficult to manage economically. There is a need to propose new solutions to eliminate these tailbacks so on to elevate the cyanobacterial biorefinery to be an economically feasible, minimum waste generating multiproduct biorefinery. Cost-effective approaches implemented from production to downstream processing without affecting the quality of products will be beneficial for attaining economic viability. The integrated approaches in cultivation systems as well as downstream processing, by simplifying individual processes to unit operation systems can obviously increase the economic feasibility to a certain extent. Low cost approaches for biomass production, multiparameter optimization and successive sequential retrieval of multiple value-added products according to their high to low market value from a biorefinery is possible. The nanotechnological approaches in cyanobacterial biorefineries make it one step closer to the goal. The current review gives an overview of strategies used for constructing self-sustainable- economically feasible- minimum waste generating; multiple products based cyanobacterial biorefineries by the efficient valorization of biomass. Also the possibility of uplifting new cyanobacterial strains for biorefineries is discussed.

Non-innocent probes in direct sonication: Metal assistance in oxidative radical CH functionalization.

Direct sonication by means of ultrasound horns constitutes a widely used technique in chemical process technology. However, the direct contact between the metal probe and the reaction mixture does not always leave the chemical system unaffected. In this report, we study the tert-butyl hydroperoxide-mediated trifluoromethylation of heterocyclic structures, and the influence of sonication thereon. Metal leaching is observed during the process and further examined, showing that several metals can interfere significantly with the chemical reaction under study. Notably, vanadium metal was found to increase the reaction rate exceptionally well, rendering it a useful additive for this type of reactions. Ultimately, some mechanistic considerations are offered, to provide more insight into the nature of the catalytic effect of leached metals.

Employing homoenolates generated by NHC catalysis in carbon-carbon bond-forming reactions: state of the art.

Homoenolate is a reactive intermediate that possesses an anionic or nucleophilic carbon ß to a carbonyl group or its synthetic equivalent. The recent discovery that homoenolates can be generated from α,ß-unsaturated aldehydes via N-Heterocyclic Carbene (NHC) catalysis has led to the development of a number of new reactions. A majority of such reactions include the use of carbon-based electrophiles, such as aldehydes, imines, enones, dienones etc. resulting in the formation of a variety of annulated as well as acyclic products. The easy availability of chiral NHCs has allowed the development of very efficient enantioselective variants of these reactions also. The tolerance showed by NHCs towards magnesium and titanium based Lewis acids has been exploited in the invention of cooperative catalytic processes. This tutorial review focuses on these and other types of homoenolate reactions reported recently, and in the process, updates the previous account published in 2008 in this journal.

NHC-catalysed annulation of enals to tethered dienones: efficient synthesis of bicyclic dienes.

Homoenolates generated from α,ß-unsaturated aldehydes using NHC catalysis underwent facile addition to dibenzylidene cyclohexanone to afford bicyclic cyclopentenes as single diastereomers.

NHC catalyzed transformation of aromatic aldehydes to acids by carbon dioxide: an unexpected reaction.

A facile NHC-mediated reaction of aromatic aldehydes with carbon dioxide leading to carboxylic acids is described. The present protocol is mechanistically important, and it can serve as a tool for the sequestration of carbon dioxide.

Nucleophilic heterocyclic carbene as a novel catalyst for cyclopropanation of cyano acrylates.

Nucleophilic heterocyclic carbenes (NHCs) have been used for the first time as catalysts in the cyclopropanation of ethyl cyanocinnamates with phenacyl bromide by Michael-initiated ring-closure (MIRC).