A refreshing cascade: General fluorocyclization reactions will breathe new life into the use of fluorinated hetero‐ and carbocycles as pharmaceuticals and agrochemicals. Allyl silanes have now been shown to undergo fluorination–cyclization with NF reagents to give cis‐ and trans‐substituted fluorinated heterocycles selectively (see scheme). The correct choice of silyl group was critical to prevent competitive fluorodesilylation.
Two experiments explored how learners allocate limited time across a set of relevant on-line texts, in order to determine the extent to which time allocation is sensitive to local task demands. The first experiment supported the idea that learners will spend more of their time reading easier texts when reading-time is more limited; the second experiment showed that readers shift preference towards harder texts when their learning goals are more demanding. These phenomena evince an impressive capability of readers. Further, the experiments reveal that the most common method of time allocation is a version of satisficing (Reader and Payne, 2007) in which preference for texts emerges without any explicit comparison of the texts (the longest time spent reading each text is on the first time that text is encountered). These experiments therefore offer further empirical confirmation for a method of time allocation that relies on monitoring on-line texts as they are read, and which is sensitive to learning goals, available time and text difficulty.
Fluorinated organic compounds constitute a significant proportion of medicines marketed today. Since heterocycles are submotifs frequently encountered in lead compounds, the corresponding fluorinated molecules that possess coupling functional groups to increase structural complexity are sought-after building blocks, especially those with stereogenic elements. To access fluoro-heterocycles, fluorocyclizations constitute an important category of reactions that permit multiple bond construction in one pot. Reactions featuring both nucleophilic and electrophilic sources of fluorine have proved valuable for the delivery of fluorinated carbo- and heterocycles. Mechanistically, two scenarios have been validated with the fluorination occurring either prior to or after the cyclization event. Fluorinated biologically active molecules prepared by employing a fluorocyclization protocol are rare, with two notable exceptions being the synthesis of fluorogypsetin and fluorobrevianamide E. Various levels of diastereocontrol were obtained with best results observed when the cyclization step precedes the fluorination. To date, asymmetric fluorocyclizations have not been explored, with the exception of a Nazarov fluorination process. In essence, this process features a catalytic asymmetric cyclization followed by a diastereoselective fluorination. Asymmetric fluoroheterocyclizations are, however, not known. For this methodology to serve medicinal chemistry, conceptual advances are essential to access fluorinated pharmacophores with programmable stereocontrol as and when necessary.
Within a globalised world that has ever changing social, economic, cultural and legal influences, higher education providers have a responsibility to equip graduates with the skills necessary to meet these demands. Pedagogic research shows that students' motivation is often driven by assessment and therefore the challenge for programmes is to find an assessment method that both assesses and encourages the development of these diverse skills set. We propose that the use of patchwork text combined with online discussion boards can facilitate critical thinking and collaborative working. This paper aims to report on the educational benefits of this combination of assessment methods to promote higher level thinking, and details the nature of the collaboration and outcomes of the assessment, providing guidance for future practise.
Frischen Wind in die Verwendung fluorierter Hetero‐ und Carbocyclen als Pharmaka und Agrochemikalien bringen allgemeine Fluorcyclisierungen. Bei Allylsilanen gelang nun die selektive Fluorierung‐Cyclisierung mit N‐F‐Reagentien zu cis‐ und trans‐substituierten fluorierten Heterocyclen (siehe Schema). Die Art der Silylgruppe entscheidet darüber, ob die konkurrierende Fluordesilylierung abläuft oder nicht.
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