Reductive Hydroformylation of Isosorbide Diallyl Ether

Isosorbide and its functionalized derivatives have numerous applications as bio-sourced building blocks. In this context, the synthesis of diols from isosorbide diallyl ether by hydrohydroxymethylation reaction is of extreme interest. This hydrohydroxymethylation, which consists of carbon-carbon double bonds converting into primary alcohol functions, can be obtained by a hydroformylation reaction followed by a hydrogenation reaction. In this study, reductive hydroformylation was achieved using isosorbide diallyl ether as a substrate in a rhodium/amine catalytic system. The highest yield in bis-primary alcohols obtained was equal to 79%.

An Efficient Synthesis of Tetrodotoxin

Tetrodotoxin (TTX) is an indispensable probe in neuroscience, a biosynthetic and ecological enigma, and one of the most celebrated targets of synthetic chemistry. Here, we present a stereoselective synthesis of TTX that proceeds in 22 steps starting from a readily available glucose derivative. The central cyclohexane ring of TTX and its α-tertiary amine moiety was established via the intramolecular 1,3-dipolar cycloaddition of a nitrile oxide, followed by alkynyl addition to the resultant isoxazoline. After some carefully chosen protecting group manipulations, a ruthenium-catalyzed hydroxylactonization set the stage for the formation of its dioxa-adamantane core. Installation of the guanidine, oxidation of a primary alcohol, and late-stage epimerization of the resultant aldehyde gave a mixture of TTX and anhydro TTX. Our synthesis represents one of the most effective of TTX reported to date and could give ready access to biologically active derivatives.

Wax Separated Effectively from Fischer-Tropsch Wax Residue by Solvent Desorption: Thermodynamic and Kinetic Analysis

The separation and recycling of effective resources in Fischer-Tropsch wax residue (FTWR) are urgent because of the environmental hazards and energy waste they bring. In this study, organic solvents are used to separate recyclable resources from FTWR efficiently, achieving the goals of “Energy Recycle” and “Fisher-Tropsch Wax Residue Treatment”. The response surface methodology (RSM) response surface analysis model accurately evaluates the relationship among temperature, residence time, liquid–solid ratio, and desorption rate and obtains the best process parameters. The results show that the product yield can reach 82.28% under the conditions of 80 °C, 4 h, and the liquid–solid ratio of 24.4 mL/g. Through the kinetic analysis of the desorption process of FTWR, the results show that the desorption process conforms to the pseudo second-order kinetic model and the internal diffusion model. The thermodynamic function results showed that there were not only van der Waals forces in the desorption process, but other strong interaction forces such as hydrogen bonds. In addition, Langmuir, Freundlich, and BET equations are used to describe the desorption equilibrium. Scanning electron microscopy (SEM) were used to analyze the pore structure of FTWR during desorption. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and Gas chromatography-mass spectrometer (GC-MS) analysis confirmed that the desorption product’s main component was hydrocarbons (50.38 wt%). Furthermore, naphthenic (22.95 wt%), primary alcohol (11.62 wt%), esters (8.7 wt%), and aromatic hydrocarbons (6.35 wt%) compounds were found and can be further purified and applied to other industrial fields. This study shows that using petroleum ether to separate and recover clean resources from Fischer-Tropsch wax residue is feasible and efficient and has potential industrial application prospects.

Biocatalyzed Flow Oxidation of Tyrosol to Hydroxytyrosol and Efficient Production of Their Acetate Esters

Tyrosol (Ty) and hydroxytyrosol (HTy) are valuable dietary phenolic compounds present in olive oil and wine, widely used for food, nutraceutical and cosmetic applications. Ty and HTy are endowed with a number of health-related biological activities, including antioxidant, antimicrobial and anti-inflammatory properties. In this work, we developed a sustainable, biocatalyzed flow protocol for the chemo- and regio-selective oxidation of Ty into HTy catalyzed by free tyrosinase from Agaricus bisporus in a gas/liquid biphasic system. The aqueous flow stream was then in-line extracted to recirculate the water medium containing the biocatalyst and the excess ascorbic acid, thus improving the cost-efficiency of the process and creating a self-sufficient closed-loop system. The organic layer was purified in-line through a catch-and-release procedure using supported boronic acid that was able to trap HTy and leave the unreacted Ty in solution. Moreover, the acetate derivatives (TyAc and HTyAc) were produced by exploiting a bioreactor packed with an immobilized acyltransferase from Mycobacterium smegmatis (MsAcT), able to selectively act on the primary alcohol. Under optimized conditions, high-value HTy was obtained in 75% yield, whereas TyAc and HTyAc were isolated in yields of up to 80% in only 10 min of residence time.