Upgrading Lignocellulosic Products to Drop-In Biofuels via Dehydrogenative Cross-Coupling and Hydrodeoxygenation Sequence

Life-cycle analysis (LCA) allows the scientific community to identify the sources of greenhouse gas (GHG) emissions of novel routes to produce renewable fuels. Herein, we integrate LCA into our investigations of a new route to produce drop-in diesel/jet fuel by combining furfural, obtained from the catalytic dehydration of lignocellulosic pentose sugars, with alcohols that can be derived from a variety of bio- or petroleum-based feedstocks. As a key innovation, we developed recyclable transition-metal-free hydrotalcite catalysts to promote the dehydrogenative cross-coupling reaction of furfural and alcohols to give high molecular weight adducts via a transfer hydrogenation- aldol condensation pathway. Subsequent hydrodeoxygenation of adducts over Pt/NbOPO4 yields alkanes. Implemented in a Brazilian sugarcane biorefinery such a process could result in a 53-79% reduction in life-cycle GHG emissions relative to conventional petroleum fuels and provide a sustainable source of low carbon diesel/jet fuel

Novel pathways for fuels and lubricants from biomass optimized using life-cycle greenhouse gas assessment

Decarbonizing the transportation sector is critical to achieving global climate change mitigation. Although biofuels will play an important role in conventional gasoline and diesel applications, bioderived solutions are particularly important in jet fuels and lubricants, for which no other viable renewable alternatives exist. Producing compounds for jet fuel and lubricant base oil applications often requires upgrading fermentation products, such as alcohols and ketones, to reach the appropriate molecular-weight range. Ketones possess both electrophilic and nucleophilic functionality, which allows them to be used as building blocks similar to alkenes and aromatics in a petroleum refining complex. Here, we develop a method for selectively upgrading biomass-derived alkyl methyl ketones with >95% yields into trimer condensates, which can then be hydrodeoxygenated in near-quantitative yields to give a new class of cycloalkane compounds. The basic chemistry developed here can be tailored for aviation fuels as well as lubricants by changing the production strategy. We also demonstrate that a sugarcane biorefinery could use natural synergies between various routes to produce a mixture of lubricant base oils and jet fuels that achieve net life-cycle greenhouse gas savings of up to 80%. biofuels | lubricants | life cycle assessment | methyl ketones | greenhouse gases C ountries around the world are enacting legislation to curb greenhouse gas (GHG) emissions. Strategies for decarbonizing road transportation include an array of options from improving engine efficiency and blending bioethanol/biodiesel with gasoline/diesel to using plug-in electric vehicles (1-3). Aviation fuels pose a unique problem because stringent specifications require oxygen-free compounds, limiting the options available (4). Biofuel solutions such as farnesane have been proposed; however, these offer only modest GHG reduction benefits (SI Appendix) and the wide boiling range requirement for jet fuels sets a limit on the amount of single-component renewable fuels that may be blended. At the other end of the spectrum are automotive lubricant base oils where a narrow range of compounds is highly desirable. Poly-α-olefins (PAOs) containing 30 carbon atoms obtained from oligomerization of fossil-derived 1-decene are considered as the benchmark of superior performance for crankcase oils and have a high demand (5). Importantly, the GHG footprint associated with PAO base oils can be higher on a per-mass basis than petroleum-derived fuels if even a fraction of the lubricant is repurposed as fuel at its end of life (6). The goal of our work was to develop a strategy for the flexible production of jet fuels and lubricant base oils in a Brazilian sugarcane refinery designed to achieve a meaningful reduction in life-cycle GHG emissions. Our approach involves conversion of sugars in sugarcane-derived sucrose and hemicellulose to ketones using a combination of chemical and biocatalytic processes. For example, 2-butanone, can be obtained by the dehydration of fermentation-derived 2,3-butanediol (7, 8) or via chemical/biochemical (9, 10) decarboxylation of levulinic acid (11). The fermentation of various biomass-derived sugars using Clostridia strains produces a mixture of acetone, butanol, and ethanol (ABE), which can be used to synthesize a mixture of monoalkylated/dialkylated ketones (12), specifically 2-pentanone and 2-heptanone. Additional synthons may be produced from bioalcohol-derived olefins (13) or biomass-derived furanic platform molecules, such as 2,5-dimethylfuran and 2-methylfuran, via hydrogenolysis to produce 2-hexanone and 2-pentanone, respectively, with as high as 98% selectivity Results and Discussion We begin by identifying heterogeneous catalysts and appropriate reaction conditions for the self-condensation of ketones (1) to produce dimer/trimer condensates 2-4 in high overall yield Significance The development of renewable liquid fuels and bioproducts is critical to reducing global reliance on petroleum and mitigating climate change, particularly for applications where few lowcarbon alternatives exist. We combine chemical catalysis with life-cycle greenhouse gas (GHG) modeling to create a new platform for producing biobased aviation fuel and automotive lubricant base oils. The recyclable catalysts we developed are capable of converting sugar and biomass-derived alkyl methyl ketones into cyclic enones via condensation reactions. These products can subsequently be hydrodeoxygenated to create a new class of aviation fuel and lubricant candidates with superior cold flow properties, density, and viscosity that substantially reduce GHG emissions relative to conventional petroleum

Synthetic studies towards the total synthesis of lancifodilactone G

This thesis presents our studies towards the first total synthesis of the novel anti- HIV agent lancifodilactone G, which has a highly unusual aliphatic enol. The first chapter provides a survey of architecturally diverse nortriterpenoids that were isolated from the Schisandraceae family. A proposed biosynthetic pathway for lancifodilactone G and closely related natural products provides a rationale for the formation of the consecutive 7/8/5 fused carbo cycles that are unique to Schisandra nortriterpenoids. Chapter 1 goes on to outline the reported strategies to access the core of lancifodilactone G and concludes with a retrosynthetic analysis proposed by the Evans group, which includes a biosynthetically inspired single-pot polycyclisation reaction. Chapter 2 describes the highly stereocontrolled synthesis of the eastern fragment (F-G rings) using transition metal-mediated Pauson-Khand reaction. This chapter also reviews the metal-mediated diastereoselective Pauson-Khand reaction directed by the stereogenic centre at C2, with the ample illustration to total synthesis. Attempted strategies for the assembly of the bicyclic cyclopentanone motif via a dienyl Pauson-Khand reaction of silicon- and oxygen- tethered diene-enes are presented. The failure of these strategies at different stages of the synthesis resulted in the exploration of a classical Pauson-Khand approach, which successfully furnished the eastern fragment. Finally, a second-generation synthesis is described which provided the fully functionalised eastern fragment with improved efficiency and overall yield. Chapter 3 discusses the successful synthesis of the western fragment (B-C rings) using a diastereoselective [4+3] cycloaddition strategy. Attempted strategies for the synthesis of the key 2,3-disubstituted furan derivative are presented, which was achieved via a hetero Pauson- Khand reaction. This chapter includes a brief account of the classical [4+3] cycloaddition reactions of furans using an in situ generated oxyallyl cation and also employing vinyl carbenoids in the metal-catalysed version. The review also highlights the application of the [4+ 3] cycloaddition reaction in the expeditious assembly of functionalised 7-membered rings that occur in a number of important biologically active natural products. The third chapter goes on to describe the application of these cycloaddition reactions in the synthesis of the fully functionalised western fragment of Lancifodilactone G. Chapter 4 describes a model study aimed at expediting the synthesis of the western fragment using a rhodium-catalysed allylic substitution reaction. A brief mechanistic discussion on unique aspects of the allylic alkylation reaction is illustrated. Chapter 4 concludes by outlining the coupling strategy for eastern and western fragments and the end game studies for the completion of the synthesis of lancifodilactone G.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

Co-production of acetone and ethanol with molar ratio control enables production of improved gasoline or jet fuel blends.

The fermentation of simple sugars to ethanol has been the most successful biofuel process to displace fossil fuel consumption worldwide thus far. However, the physical properties of ethanol and automotive components limit its application in most cases to 10-15 vol% blends with conventional gasoline. Fermentative co-production of ethanol and acetone coupled with a catalytic alkylation reaction could enable the production of gasoline blendstocks enriched in higher-chain oxygenates. Here we demonstrate a synthetic pathway for the production of acetone through the mevalonate precursor hydroxymethylglutaryl-CoA. Expression of this pathway in various strains of Escherichia coli resulted in the co-production of acetone and ethanol. Metabolic engineering and control of the environmental conditions for microbial growth resulted in controllable acetone and ethanol production with ethanol:acetone molar ratios ranging from 0.7:1 to 10.0:1. Specifically, use of gluconic acid as a substrate increased production of acetone and balanced the redox state of the system, predictively reducing the molar ethanol:acetone ratio. Increases in ethanol production and the molar ethanol:acetone ratio were achieved by co-expression of the aldehyde/alcohol dehydrogenase (AdhE) from E. coli MG1655 and by co-expression of pyruvate decarboxylase (Pdc) and alcohol dehydrogenase (AdhB) from Z. mobilis. Controlling the fermentation aeration rate and pH in a bioreactor raised the acetone titer to 5.1 g L(-1) , similar to that obtained with wild-type Clostridium acetobutylicum. Optimizing the metabolic pathway, the selection of host strain, and the physiological conditions employed for host growth together improved acetone titers over 35-fold (0.14-5.1 g/L). Finally, chemical catalysis was used to upgrade the co-produced ethanol and acetone at both low and high molar ratios to higher-chain oxygenates for gasoline and jet fuel applications. Biotechnol. Bioeng. 2016;113: 2079-2087. © 2016 Wiley Periodicals, Inc

Catalytic upgrading of biomass-derived methyl ketones to liquid transportation fuel precursors by an organocatalytic approach.

A highly efficient water-tolerant, solid-base catalyst for the self-condensation of biomass-derived methyl ketones to jet-diesel fuel precursors was developed by grafting site-isolated secondary amines on silica-alumina supports. It is shown that apart from the nature and density of amine groups and the spatial separation of the acidic and basic sites, the acidity of the support material plays a critical role in defining the catalytic activity. It is also found that a combination of weakly acidic silanol/aluminol with secondary amine groups can mimic proline catalysts and are more effective in catalyzing the selective dimerization reaction than the combination of amines with organic acids. In situ FTIR measurements demonstrate that acidic groups activate methyl ketones through their carbonyl groups leading to a favorable CC bond formation step involving an enamine intermediate. DFT analysis of the reaction pathway confirms that CC bond formation is the rate-limiting step