Engineered yeast tolerance enables efficient production from toxified lignocellulosic feedstocks

Lignocellulosic biomass remains unharnessed for the production of renewable fuels and chemicals due to challenges in deconstruction and the toxicity its hydrolysates pose to fermentation microorganisms. Here, we show in Saccharomyces cerevisiae that engineered aldehyde reduction and elevated extracellular potassium and pH are sufficient to enable near-parity production between inhibitor-laden and inhibitor-free feedstocks. By specifically targeting the universal hydrolysate inhibitors, a single strain is enhanced to tolerate a broad diversity of highly toxified genuine feedstocks and consistently achieve industrial-scale titers (cellulosic ethanol of >100 grams per liter when toxified). Furthermore, a functionally orthogonal, lightweight design enables seamless transferability to existing metabolically engineered chassis strains: We endow full, multifeedstock tolerance on a xylose-consuming strain and one producing the biodegradable plastics precursor lactic acid. The demonstration of “drop-in” hydrolysate competence enables the potential of cost-effective, at-scale biomass utilization for cellulosic fuel and nonfuel products alike.

O-Functionalised NHC Ligands for Efficient Nickel-catalysed C–O Hydrosilylation

A series of C,O-bidentate chelating mesoionic carbene nickel(ii) complexes [Ni(NHC^PhO)2] (NHC = imidazolylidene or triazolylidene) were applied for hydrosilylation of carbonyl groups. The catalytic system is selective towards aldehyde reduction and tolerant to electron-donating and -withdrawing group substituents. Stoichiometric experiments in the presence of different silanes lends support to a metal–ligand cooperative activation of the Si–H bond. Catalytic performance of the nickel complexes is dependent on the triazolylidene substituents. Butyl-substituted triazolylidene ligands impart turnover numbers up to 7,400 and turnover frequencies of almost 30,000 h-1, identifying this complex as one of the best-performing nickel catalysts for hydrosilylation and demonstrating the outstanding potential of O-functionalised NHC ligands in combination with first-row transition metals.

Reduction of Aldehydes Using Sodium Borohydride under Ultrasonic Irradiation

A simple, energy efficient, and relatively quick synthetic procedure for the reduction of aldehydes under ultrasonic irradiation is reported. Satisfactorily isolated yields (71-96%) were achieved confirming that the preparation of alcohol by aldehyde reduction is possible in green and sustainable fashion.

Metal-free disproportionation of formic acid mediated by organoboranes

In the presence of dialkylboranes, formic acid is converted to formaldehyde and methanol derivatives. This is the first example of formate disproportionation under metal-free conditions. Mechanistic studies highlight the role of transient borohydrides in the reduction of formates and this is further shown in transfer hydroboration for aldehyde reduction.