N-Triflylphosphorimidoyl Trichloride: A Versatile Reagent for the Synthesis of Strong Chiral Brønsted Acids

A series of strong Brønsted acids has been synthesized in high yields using N-triflylphosphorimidoyl trichloride as reagent. The syntheses proceed efficiently with electron-rich, electron-deficient, and sterically hindered substrates

Strong and Confined Acids Enable a Catalytic Asymmetric Nazarov Cyclization of Simple Divinyl Ketones

We report a catalytic asymmetric Nazarov cyclization of simple, acylic, alkyl-substituted divinyl ketones using our recently disclosed strong and confined imidodiphosphorimidate Brønsted acids. The corresponding monocyclic cyclopentenones are formed in good yields and excellent regio-, diastereo-, and enantioselectivities. Further, the chemical utility of the obtained enantiopure cyclopentenones is demonstrated

The Professional Development of School Social Workers

The purpose of this study was to examine the characteristics of continuing professional education, professional development, and other growth activities that most heavily influence the practice of school social workers. It was a qualitative study framed by heuristic inquiry using in depth interviews with twenty participants from two western states. A theoretical model emerged based on three components: the context of practice, contextual learning, and practice behaviors. All three components had the same three attributes: prior learning experiences, outside learning experiences, and the personal qualities of practitioners. Two important findings were that when the participants covered only one school and were funded by multiple sources, they were able to conduct more systemically-oriented interventions than would otherwise have been possible

A Chiral, Dendralenic C–H Acid

We report the synthesis of a chiral dendralenic C–H acid, which contains three unsubstituted binaphthyl moieties. This motif and an achiral variant can be made from their corresponding bis(sulfone) precursors in one step. Despite the presence of the enantiopure binaphthyl backbone, the newly designed chiral C–H acid showed only poor enantioselectivity in a Mukaiyama aldol reaction. First attempts toward the synthesis of 3,3′-hexasubstituted binaphthyl-based dendralenic acids are also reported

Organocatalysis emerging as a technology

During the last 20 years, organocatalysis has significantly advanced as a field. Thanks to contributions from hundreds of groups and companies around the world, the area has risen from a few mechanistically ill-defined niche reactions, to one of the most vibrant and innovative fields in chemistry, providing several well-defined generic activation modes for selective catalysis. Organocatalysis is also on the rise in industrial settings, especially for the production of enantiomers, which are of use in fine chemistry, pharma, crop-protection, and fragrance chemistry. Here we will look at some of the specific elements of organocatalysis that we think are particularly attractive and contribute to this successful development

Azine Activation via Silylium Catalysis

Practical, efficient, and general methods for the diversification of N-heterocycles have been a recurrent goal in chemical synthesis due to the ubiquitous influence of these motifs within bioactive frameworks. Here, we describe a direct, catalytic, and selective functionalization of azines via silylium activation. Our catalyst design enables mild conditions and a remarkable functional group tolerance in a one-pot setup

Transmembrane potential polarization, calcium influx, and receptor conformational state modulate the sensitivity of the imidacloprid-insensitive neuronal insect nicotinic acetylcholine receptor to neonicotinoid insecticides

Neonicotinoid insecticides act selectively on insect nicotinic acetylcholine receptors (nAChRs). Recent studies revealed that their efficiency was altered by the phosphorylation/dephosphorylation process and the intracellular signaling pathway involved in the regulation of nAChRs. Using whole-cell patch-clamp electrophysiology adapted for dissociated cockroach dorsal unpaired median (DUM) neurons, we demonstrated that intracellular factors involved in the regulation of nAChR function modulated neonicotinoid sensitivity. DUM neurons were known to express two alpha-bungarotoxin-insensitive nAChR subtypes: nAChR1 and nAChR2. Whereas nAChR1 was sensitive to imidacloprid, nAChR2 was insensitive to this insecticide. Here, we demonstrated that, like nicotine, acetamiprid and clothianidin, other types of neonicotinoid insecticides, acted as agonists on the nAChR2 subtype. Using acetamiprid, we revealed that both steady-state depolarization and hyperpolarization affected nAChR2 sensitivity. The measurement of the input membrane resistance indicated that change in the acetamiprid-induced agonist activity was related to the receptor conformational state. Using cadmium chloride, omega-conotoxin GVIA, and (R,S)-(3,4-dihydro-6,7-dimethoxy-isoquinoline-1-yl)-2-phenyl-N,N-di-acetamide (LOE 908), we found that inhibition of calcium influx through high voltage-activated calcium channels and transient receptor potential gamma (TRPgamma) activated by both depolarization and hyperpolarization increased nAChR2 sensitivity to acetamiprid. Finally, using N-(6-aminohexyl)-5-chloro-1-naphthalenesulfonamide hydrochloride (W7), forskolin, and cAMP, we demonstrated that adenylyl cyclase sensitive to the calcium/calmodulin complex regulated internal cAMP concentration, which in turn modulated TRPgamma function and nAChR2 sensitivity to acetamiprid. Similar TRPgamma-induced modulatory effects were also obtained when clothianidin was tested. These findings bring insights into the signaling pathway modulating neonicotinoid efficiency and open novel strategies for optimizing insect pest control