Plant species' range shifts in mountainous areas—all uphill from here?

Species from many different habitats are responding to recent climate change. Mountainous areas are of particular interest as they provide pronounced gradients and have experienced above-average temperature increases. Data from the beginning of the 20th century of both the upper and lower range limits of plants of the European Alps were updated a century later and analyzed in order to identify common trends and deviating patterns of shifts at opposing ends of species' ranges. At the upper limit, there was a strong trend towards an increase in species richness per summit, including 33 species that were recorded for the first time on any of the investigated summit areas. The species experienced a consistent upward shift exceeding 100 elevational meters, and 49 out of the 125 investigated species shifted upwards to a present altitude which is higher than any reported occurrence in the region one century ago. The response at the lower range limit was more heterogeneous and suggests species-specific differences in responsiveness and response patterns. With this approach of the combined analysis of upper and lower range limits along elevational gradients, it is possible to identify candidate species that might not keep pace with climate change, and thus, might face an increased risk of extinction with continued global warmin

A Highly Chemoselective and Practical Alkynylation of Thiols

A thiol-alkynylation procedure utilizing the hypervalent iodine alkyne transfer reagent TIPS-ethynyl-benziodoxolone has been developed. This scalable reaction proceeds in five minutes at room temperature in an open flask using commercially available reagents. The scope of the reaction is broad, with a variety of phenolic, benzylic, heterocyclic, and aliphatic thiols undergoing alkynylation in excellent yield. The method is highly chemoselective as a vast array of functional groups are tolerated. The utility of the thiol-alkynylation in postsynthetic elaboration has been demonstrated through the facile installment of a fluorophore tag on a cysteine-containing peptide

General and Practical Formation of Thiocyanates from Thiols

A new method for the cyanation of thiols and disulfides using cyanobenziodoxol(on)e hypervalent iodine reagents is described. Both aliphatic and aromatic thiocyanates can be accessed in good yields in a few minutes at room temperature starting from a broad range of thiols with high chemioselectivity. The complete conversion of disulfides to thiocyanates was also possible. Preliminary computational studies indicated a low energy concerted transition state for the cyanation of the thiolate anion or radical. The developed thiocyanate synthesis has broad potential for various applications in synthetic chemistry, chemical biology and materials science

Total Synthesis and Biological Evaluation of Jerantinine E

The first total synthesis of the alkaloid natural product jerantinine E is based on a selective cyclization of an aminocyclopropane. Preliminary investigations show that it inhibits the polymerization of tubulin, displaying significant cytotoxicity and antimigratory activity against both breast and lung cancer cell lines

Fast and Highly Chemoselective Alkynylation of Thiols with Hypervalent Iodine Reagents Enabled through a Low Energy Barrier Concerted Mechanism

Among all functional groups, alkynes occupy a privileged position in synthetic and medicinal chemistry, chemical biology, and materials science. Thioalkynes, in particular, are highly useful, as they combine the enhanced reactivity of the triple bond with a sulfur atom frequently encountered in bioactive compounds and materials. Nevertheless, general methods to access these compounds are lacking. In this article, we describe the mechanism and full scope of the alkynylation of thiols using ethynyl benziodoxolone (EBX) hypervalent iodine reagents. Computations led to the discovery of a new, three-atom concerted transition state with a very low energy barrier, which rationalizes the high reaction rate. On the basis of this result, the scope of the reaction was extended to the synthesis of aryl- and alkyl-substituted alkynes containing a broad range of functional groups. New sulfur nucleophiles such as thioglycosides, thioacids, and sodium hydrogen sulfide were also alkynylated successfully to lead to the most general and practical method yet reported for the synthesis of thioalkynes

Taming Hypervalent Bonds and Strained Rings for Catalysis and Synthesis

Improving the synthesis of complex organic molecules is essential for progress in many fields such as medicine, agrochemicals or materials. Since 2007, our laboratory has been focusing on the development of non-classical bond disconnections based on the use of small, energy-loaded organic molecules: hypervalent iodine reagents and strained rings. In this overview article, we report our progress since 2011 in these areas. The use of cyclic hypervalent iodine reagents has been extended to the C2-selective alkynylation of indoles, the domino cyclization alkynylation of allenes, the alkynylation of thiols and the azidation of carbonyl compounds. Amino-substituted aminocyclopropanes and aminocyclobutanes were used in [3+2] and [4+2] annulations to access nitrogen-rich building blocks, including nucleoside analogues. The first example of dynamic kinetic [3+2] annulation of aminocyclopropanes with both enol ethers and aldehydes was also reported

Plant species’ range shifts in mountainous areas—all uphill from here?

Species from many different habitats are responding to recent climate change. Mountainous areas are of particular interest as they provide pronounced gradients and have experienced above-average temperature increases. Data from the beginning of the 20th century of both the upper and lower range limits of plants of the European Alps were updated a century later and analyzed in order to identify common trends and deviating patterns of shifts at opposing ends of species' ranges. At the upper limit, there was a strong trend towards an increase in species richness per summit, including 33 species that were recorded for the first time on any of the investigated summit areas. The species experienced a consistent upward shift exceeding 100 elevational meters, and 49 out of the 125 investigated species shifted upwards to a present altitude which is higher than any reported occurrence in the region one century ago. The response at the lower range limit was more heterogeneous and suggests species-specific differences in responsiveness and response patterns. With this approach of the combined analysis of upper and lower range limits along elevational gradients, it is possible to identify candidate species that might not keep pace with climate change, and thus, might face an increased risk of extinction with continued global warmin

A Highly Chemoselective and Practical Alkynylation of Thiols

A thiol-alkynylation procedure utilizing the hypervalent iodine alkyne transfer reagent TIPS-ethynyl-benziodoxolone has been developed. This scalable reaction proceeds in five minutes at room temperature in an open flask using commercially available reagents. The scope of the reaction is broad, with a variety of phenolic, benzylic, heterocyclic, and aliphatic thiols undergoing alkynylation in excellent yield. The method is highly chemoselective as a vast array of functional groups are tolerated. The utility of the thiol-alkynylation in postsynthetic elaboration has been demonstrated through the facile installment of a fluorophore tag on a cysteine-containing peptide

Neue Daten zum Monitoring alpiner Pflanzen im Engadin

During the summers of 2004 and 2005, the mountain flora of Piz Languard (3262 m a.s.l.) near Pontresina (Switzerland) was monitored and compared to the inventories from the years 1905, 1907, 1941, 1985 and 2003. The occurrence of flowering plants above 3000 m has been recorded with a standard deviation of ± 10 m. Trends, detected in earlier years, in the upward shift of alpine plants on Piz Languard has again been confirmed. Whereas 37 plant species have shown a clear upward shift during the last decades, there are 36 more or less stationary species and 12 species have moved to slightly lower altitudes. The highest amount of upward shift has been show by the following plant species: Lotus alpinus, Arnica montana, Adeno- styles leucophylla, Artemisia umbelliformis, Vaccinium vitis-idaea, Salix serpyllifolia and Lloydia serotina. Since ca. 1985 there has been an accelerated upward shift of approximately 10 m per decade. Furthermore, in the wider region of Bernina and Lower Engadine, the uppermost occur- rence of flowering plants and ferns has been recorded with the help of historical data from the following years: 1573-2001, 1982-2002 and 2003-2005. In the tributary valley of Tasna, 213 plant species from a total of 980 show an upward shift of more than a 100 m during the last decades