Mechanochemical Organocatalysis: Do High Enantioselectivites Contradict what we Might Expect?

Ball mills input energy to samples by pulverising the contents of the jar. Each impact on the sample or wall of the jar results in an instantaneous transmission of energy in the form of a temperature and pressure increase (volume reduction). Conversely, enantioselective organocatalytic reactions proceed through perceived delicate and well-organised transition states. Does there exist a dichotomy in the idea of enantioselective mechanochemical organocatalysis? This Review provides a survey of the literature reporting the combination of organocatalytic reactions with mechanochemical ball milling conditions. Where possible, direct comparisons of stirred in solution, stirred neat and ball milled processes are drawn with a particular focus on control of stereoselectivity

Expedient Organocatalytic Aza-Morita–Baylis–Hillman Reaction through Ball-Milling

A ball-milling enabled tertiary amine catalyzed aza-Morita–Baylis–Hillman reaction is reported. The reaction process does not require solvent, has significantly shorter reaction times than previous methods and is reported on a range of imines and acrylate Michael acceptors across than 26 examples. A 12-fold scaled-up example is also reported as well as experimental comparisons to solution-based experiments and neat-stirred reactions

Manganese-Catalyzed Electrochemical Deconstructive Chlorination of Cycloalkanols via Alkoxy Radicals

A manganese-catalyzed electrochemical deconstructive chlorination of cycloalkanols has been developed. This electrochemical method provides access to alkoxy radicals from alcohols and exhibits a broad substrate scope, with various cyclopropanols and cyclobutanols converted into synthetically useful β- and γ-chlorinated ketones (40 examples). Furthermore, the combination of recirculating flow electrochemistry and continuous inline purification was employed to access products on a gram scale

Acquisition of Ca2+ and HCO3−/CO32− for shell formation in embryos of the common pond snail Lymnaea stagnalis

Embryos of the freshwater common pond snail Lymnaea stagnalis develop to hatch within 10 days under control conditions (22°C, Miami-Dade tap water) and this development is impaired by removal of ambient calcium. In contrast, embryos did not exhibit dependence upon an ambient HCO3−/CO32− source, developing and hatching in HCO3−/CO32−-free water at rates comparable to controls. Post-metamorphic, shell-laying embryos exhibited a significant saturation-type calcium uptake as a function of increasing ambient calcium concentration. However, changes in ambient bicarbonate concentration did not influence calcium or apparent titratable alkalinity uptake. There was a distinct shift from no significant flux in pre-metamorphic embryos to net uptake of calcium in post-metamorphic stages as indicated by an increased uptake from the micro-environment surrounding the egg mass and increased net uptake in 24-h, whole egg mass flux measurements. Furthermore, HCO3−/CO32− acquisition as measured by titratable alkalinity flux is at least partially attributable to an endogenous carbonate source that is associated with acid extrusion. Thus, calcium requirements for embryonic shell formation are met via uptake but HCO3−/CO32−, which is also necessary for shell formation is acquired in part from endogenous sources with no detectable correlation to ambient HCO3−/CO32− availability

Change & Maintaining Change in School Cafeterias: Economic and Behavioral-Economic Approaches to Increasing Fruit and Vegetable Consumption

Developing a daily habit of consuming fruits and vegetables (FV) in children is an important public-health goal. Eating habits acquired in childhood are predictive of adolescent and adult dietary patterns. Thus, healthy eating patterns developed early in life can protect the individual against a number of costly health deficits and may reduce the prevalence of obesity. At present, children in the United States (US) under-consume FV despite having access to them through the National School Lunch Program. Because access is an obstacle to developing healthy eating habits, particularly in low-income households, targeting children’s FV consumption in schools has the advantage of near-universal FV availability among more than 30 million US children. This chapter reviews economic and behavioral-economic approaches to increasing FV consumption in schools. Inclusion criteria include objective measurement of FV consumption (e.g., plate waste measures) and minimal demand characteristics. Simple but effective interventions include (a) increasing the variety of vegetables served, (b) serving sliced instead of whole fruits, (c) scheduling lunch after recess, and (d) giving children at least 25 minutes to eat. Improving the taste of FV and short-term incentivizing consumption of gradually increasing amounts can produce large increases in consumption of these foods. Low-cost game-based incentive program may increase the practicality of the latter strategy

Recent Advances in Catalysis Using Organoborane-Mediated Hydride Abstraction

C-H functionalization is widely regarded as an important area in the development of synthetic methodology, enabling the design of more time- and atom-efficient syntheses. The ability of electron-deficient organoboranes to mediate hydride abstraction from α-amino C?H bonds is therefore of great interest, as the reactive iminium and hydridoborate moieties generated are able to participate in a range of synthetically useful transformations. In this review update, we cover the recent advances made in organoborane mediated hydride abstraction, with particular focus on the catalytic applications of electron deficient boranes for α- or β- functionalization, α,β-difunctionalization, and the dehydrogenation of amines.</p