In contrast to the very large number of special methods applicable to syntheses in the heterocyclic series, relatively few general methods are available. The 1,3-dipolar addition offers a remarkably wide range of utility in the synthesis of five-membered heterocycles. Here the “1,3-dipole”, which can only be represented by zwitterionic octet resonance structures, combines in a cycloaddition with a multiple bond system – the “dipolarophile” – to form an uncharged five-membered ring. Although numerous individual examples of this reaction were known, some even back in the nineteenth century, fruitful development of this synthetic principle has been achieved only in recent years.

1,3-Dipolar Cycloadditions. Past and Future†

Over the past decade, the most significant, conceptual advances in the field of fluorination were enabled most prominently by organo- and transition-metal catalysis. The most challenging transformation remains the formation of the parent C-F bond, primarily as a consequence of the high hydration energy of fluoride, strong metal-fluorine bonds, and highly polarized bonds to fluorine. Most fluorination reactions still lack generality, predictability, and cost-efficiency. Despite all current limitations, modern fluorination methods have made fluorinated molecules more readily available than ever before and have begun to have an impact on research areas that do not require large amounts of material, such as drug discovery and positron emission tomography. This Review gives a brief summary of conventional fluorination reactions, including those reactions that introduce fluorinated functional groups, and focuses on modern developments in the field.

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Introduction of Fluorine and Fluorine-Containing Functional Groups

Endophytic microorganisms are to be found in virtually every plant on earth. These organisms reside in the living tissues of the host plant and do so in a variety of relationships ranging from symbiotic to pathogenic. Endophytes may contribute to their host plant by producing a plethora of substances that provide protection and ultimately survival value to the plant. Ultimately, these compounds, once isolated and characterized, may also have potential for use in modern medicine, agriculture, and industry. Novel antibiotics, antimycotics, immunosuppressants, and anticancer compounds are only a few examples of what has been found after the isolation and culturing of individual endophytes followed by purification and characterization of some of their natural products. The prospects of finding new drugs that may be effective candidates for treating newly developing diseases in humans, plants, and animals are great. Other applications in industry and agriculture may also be discovered among the novel products produced by endophytic microbes.

Natural products from endophytic microorganisms.

A list of 1719 chemical compounds identified from headspace samples of floral scent is presented. The list has been compiled from some 270 published papers, including analyses of 991 species of flowering plants and a few gymnosperms, a sample including seed plants from 90 families and 38 orders. The compounds belong to seven major compound classes, of which the aliphatics, the benzenoids and phenylpropanoids, and, among the terpenes, the mono- and sesquiterpenes, occur in most orders of seeds plants. C5-branched compounds, irregular terpenes, nitrogen-containing compounds, and a class of miscellaneous cyclic compounds have been recorded in about two-thirds of the orders. Sulfur-containing compounds occur in a third of the orders, whereas diterpenes have been reported from three orders only. The most common single compounds in floral scent are the monoterpenes limonene, (E)-β-ocimene, myrcene, linalool, α- and β-pinene, and the benzenoids benzaldehyde, methyl 2-hydroxybenzoate (methyl salicylate), benzyl alcohol, and 2-phenyl ethanol, which occur in 54–71% of the families investigated so far. The sesquiterpene caryophyllene and the irregular terpene 6-methyl-5-hepten-2-one are also common and occur in more than 50% of the families. Orchidaceae are by far the best investigated family, followed by several families known to have many species with strongly scented flowers, such as Araceae, Arecaceae, Magnoliaceae, and Rosaceae. However, the majority of angiosperm families are still poorly investigated. Relationships between floral scent and pollination, chemistry, evolution, and phylogeny are briefly discussed. It is concluded that floral scent chemistry is of little use for phylogenetic estimates above the genus level, whereas the distribution and combinations of floral scent compounds at species and subspecific levels is a promising field of investigation for the understanding of adaptations and evolutionary processes in angiosperms.

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Diversity and Distribution of Floral Scent

Einer sehr grosen Zahl spezieller Synthesewege in die heterocyclische in die Reihe steht ein nur bescheidener Satz an Aufbaumethoden von allgemeiner Verwendbarkeit gegenuber. Eine erstaunliche Anwendungsbreite bei der Synthese funfgliedriger Heterocyclen kommt der 1.3-Dipolaren Addition zu. Dabei vereinigt sich der nur mit zwitterionischen Oktett-Grenzformeln wiederzugebende „1.3-Dipol” mit einem Mehrfachbindungssystem, dem „Dipolarophil”, in einer Cycloaddition zum ladungsfreien funfgliedrigen Ring. Wenngleich die Kenntnis zahlreicher Einzelbeispiele bis ins vorige Jahrhundert zuruckreicht, gelangte das Syntheseprinzip erst in den letzten Jahren zu fruchtbarer Entfaltung.

1.3‐Dipolare Cycloadditionen Rückschau und Ausblick

Structure, synthesis, and chemical reactions of fluorinated cyclopropanes and cyclopropenes.

Highly substituted carbocyclic seven-membered rings are frequently found in natural products and their synthesis represents a significant challenge to the synthetic chemist. Direct intramolecular cyclization of these systems often proves difficult and this fact has catalyzed the development of a variety of strategies based on a convergent intermolecular cycloaddition strategy. This concept article discusses the major cycloaddition approaches utilized to access these types of structures and primarily focuses on examples employed in the synthesis of natural products.

The cycloaddition strategy for the synthesis of natural products containing carbocyclic seven-membered rings.

Photocyclization of aryl-substituted acetylenesi application of di-.pi.-methane-like rearrangements to arylcyclopropene syntheses

Confocal microscopy with Zinquin, a fluorogenic Zn2+-specific indicator, was used for spatially and temporally resolved measurement of Zn2+ efflux from single pancreatic β-cells. When cells were incubated in buffer containing Zinquin, application of insulin secretagogues evoked an increase in fluorescence around the surface of the cell, indicative of detection of Zn2+ efflux from the cell. The fluorescence increases corresponded spatially and temporally with measurements of exocytosis obtained simultaneously by amperometry. When images were taken at 266-ms intervals, the detection limit for Zn2+ was ∼0.5 μM. With this image frequency, it was possible to observe bursts of fluorescence which were interpreted as fluctuations of Zn2+ level due to exocytosis. The average intensity of these fluorescence bursts corresponded to a Zn2+ concentration of ∼7 μM. Since insulin is co-stored with Zn2+ in secretory vesicles, it was concluded that the Zn2+ efflux corresponded to exocytosis of insulin/Zn2+-containing granu...

Merle A. Battiste

Papers

Structure, synthesis, and chemical reactions of fluorinated cyclopropanes and cyclopropenes.

The cycloaddition strategy for the synthesis of natural products containing carbocyclic seven-membered rings.

Photocyclization of aryl-substituted acetylenesi application of di-.pi.-methane-like rearrangements to arylcyclopropene syntheses

Detection of Secretion from Single Pancreatic β-Cells Using Extracellular Fluorogenic Reactions and Confocal Fluorescence Microscopy

Trimethylsilyl fluorosulfonyldifluoroacetate (TFDA): a new, highly efficient difluorocarbene reagent