An expansion of methodologies aimed at the formation of versatile organonitriles, via the intramolecular aminocyanation of unactivated alkenes, is herein reported. Importantly, the need for a rigid tether in these reactions has been obviated. The ease-of-synthesis and viability of substrates bearing flexible backbones has permitted for diastereoselective variants as well. We demonstrated the utility of this methodology with the formation of pyrrolidones, piperidinones, isoindolinones, and sultams. Furthermore, subsequent transformation of these motifs into medicinally relevant molecules is also demonstrated. A double crossover C-labeling experiment is consistent with a fully intramolecular cyclization mechanism. Deuterium labeling experiments support a mechanism involving syn-addition across the alkene.

Alkene oxyacylation is a new strategy for the preparation of β-oxygenated ketones. Now, with Ir catalysis and low-cost salicylate esters, alkene oxyacylation can be promoted by simple and versatile hydroxyl directing groups. This paper discusses catalyst optimization, substituent effects, mechanistic experiments, and the challenges associated with asymmetric catalysis. Crossover experiments point to several key steps of the mechanism being reversible, including the most likely enantiodetermining steps. The oxyacylation products are also prone to racemization without catalyst when heated alone; however, crossover is not observed without catalyst. These observations account for the low levels of enantioinduction in alkene oxyacylation. The versatility of the hydroxyl directing group is highlighted by demonstrating further transformations of the products.

Reported herein is a diastereoselective intramolecular alkene cyanoamidation, wherein high d.r. values are imparted by chiral directing groups. Lactams with an α-all-carbon quaternary stereocenter are readily synthesized, which may enable access to structures frequently found in biologically active molecules and natural products.

The production of green gasoline, jet, and diesel biofuels from waste greases was achieved using a novel hydrothermal, continuous-flow catalytic process operating under supercritical water conditions, with recycled water the only added chemical. Thermally and chemically stable catalysts were explored to optimize yields of liquid biofuels and to minimize production of gases and acidic compounds. A 50:50 mixture of brown and yellow waste greases converted into 76.6 wt% liquid biocrude (BC); the remainder converted to water and gases. Less than 0.2% of the feedstock (FS) formed carbon char (mainly amongst catalyst particles). Various tubular reactors (Inconel, Hastelloy, titanium, stainless) showed no interior defects, erosion, or mass loss after runs. The titanium catalyst was fully recovered and regenerated back to its original potency. The BC was further refined into 28%, 48%, 20%, and 4 wt%, respectively for green gasoline, jet, diesel, and bunker. Biofuels were analyzed for compound class compositions and reaction mechanisms were proposed. Hundreds of identified fuel products (C 3 -C 35 ) from processing oleic acid as a pure model compound were identified. The neat green gasoline and diesel biofuels, along with a 50% green jet blend (with petroleum Jet A), were tested in appropriate spark ignition, turbine, and diesel engines at the University of Minnesota Engine Labs. The biofuels achieved 107.7%, 97.2%, and 101.3% engine power performance levels relative to petroleum fuels (91-Octane, Jet A, #2 Diesel) along with lower CO and pollutant emissions. The biofuels complied with American Society for Testing and Materials (ASTM) fuel specifications (D4814, D7566, D975) including mandated corrosion and low sulfur limits of all three biofuels.

Intramolecular Oxyacylation of Alkenes Using a Hydroxyl Directing Group. -Despite the application of a chiral ligand all products are obtained as racemates. Mechanistic experiments furnish evidence that the most likely enantiodetermining steps are reversible what in combination with the relatively high reaction temperature thwarts the asymmetric induction. -(HOANG, G. T.; PAN, Z.; BRETHORST, J. T.; DOUGLAS*, C. J.; J. Org. Chem. 79 (2014) 23, 11383-11394, http://dx.doi.org/10.1021/jo501814n ; Dep. Chem., Univ. Minn., Minneapolis, MN 55455, USA; Eng.) -H. Haber 19-043