Transition-Metal-Catalyzed C−S, C−Se, and C−Te Bond Formation via Cross-Coupling and Atom-Economic Addition Reactions

We review the evolution of domestic animals, emphasizing the effect of the earliest steps of domestication on its course. Using the first domesticated species, the dog (Canis familiaris), for illustration, we describe the evolutionary peculiarities during the historical domestication, such as the high level and wide range of diversity. We suggest that the process of earliest domestication via unconscious and later conscious selection of human-defined behavioral traits may accelerate phenotypic variations. The review is based on the results of a long-term experiment designed to reproduce early mammalian domestication in the silver fox (Vulpes vulpes) selected for tameability or amenability to domestication. We describe changes in behavior, morphology and physiology that appeared in the fox during its selection for tameability, which were similar to those observed in the domestic dog. Based on the data of the fox experiment and survey of relevant data, we discuss the developmental, genetic and possible molecular genetic mechanisms underlying these changes. We ascribe the causative role in evolutionary transformation of domestic animals to the selection for behavior and to the neurospecific regulatory genes it affects.

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Animal evolution during domestication: the domesticated fox as a model

The versatility and utility of vinyl chalcogenides in organic synthesis is well documented through the publication of a number of review articles1 and books.2 The development of new methods for the preparation and applicability of vinyl sulfides,3a-c sulfones,3d and tellurides4 was recently revised. * Corresponding author. Phone/fax: +55 53 3275 7533. E-mail: gelson_perin@ufpel.edu.br. Chem. Rev. 2009, 109, 1277–1301 1277

Synthesis of Vinyl Selenides

Vinylic tellurides: from preparation to their applicability in organic synthesis.

Despite different geological features the Nordic countries are generally selenium-poor areas. In each country various factors such as food importation and life-style determine the selenium (Se) intake. Due to an extremely low Se intake in the 1970s in Finland, 0.025 mg/day, an official decision was made in 1984 to supplement multinutrient fertilizers with Se in the chemical form of sodium selenate. Almost all fertilizers used in Finland since 1985 have contained Se. Currently all crop fertilizers contain 15 mg Se/kg. Finland is still the only country to take this country-wide measure. In a national monitoring programme, sampling of cereals, basic foodstuffs, feeds, fertilizers, soils, and human tissues has been carried out annually since 1985 by four governmental research organizations. Sampling of foods has been done four times per year and human blood has been obtained annually from the same (n=60) adults. The accuracy of analyses has been verified by annual interlaboratory quality control. During this programme the selenium concentration of spring cereals has increased on average 15-fold compared with the level before the Se fertilization. The mean increase in the Se concentration in beef, pork and milk was 6-, 2- and 3-fold. In terms of Se, organically grown foods of plant origin are generally comparable to products produced before the Se supplementation of fertilizers. Milk from organically fed cows is 50% lower in Se than the usual milk. The average dietary human intake increased from 0.04 mg Se/day/10 MJ in 1985 to a present plateau of 0.08 mg Se/day/10 MJ, which is well above the current nutrition recommendations. Foods of animal origin contribute over 70% of the total daily Se intake. The mean human plasma Se concentration increased from 0.89 μmol/L to a general level of 1.40 μmol/L that can be considered to be an optimal status. The absence of Se deficiency diseases and a reference population have made conclusions on the impact on human health difficult. However, the rates of cardiovascular diseases and cancers have remained similar during the pre- and post-supplementation indicating medical and life-style factors to be much stronger determinants than Se. The nationwide supplementation of fertilizers with sodium selenate is shown to be effective and safe in increasing the Se intake of the whole population. Also, the health of animals has improved.

Effects of nationwide addition of selenium to fertilizers on foods, and animal and human health in Finland: From deficiency to optimal selenium status of the population

Addition of selenium dibromide to divinyl sulfide: spontaneous rearrangement of 2,6-dibromo-1,4-thiaselenane to 5-bromo-2-bromomethyl-1,3-thiaselenolane

Sulfur-, selenium-, and nitrogen-containing compounds bearing leaving groups in the β-position undergo facile substitution chemistry enabled by anchimeric assistance. Here we provide direct comparisons between such systems in the rigid bicyclo[3.3.1]nonane framework easily derived from 1,5-cyclooctadiene. For a series of dichloride electrophiles of this type, the relative reactivities were found to be Se ≫ (alkyl)N > S ≥ (propargyl)N > (phenyl)N, with the reaction rates at the two extremes differing by more than 3 orders of magnitude. For the N-alkyl case, substitution rates were largely independent of the trapping nucleophile but were strongly dependent on solvent, showing that the process is controlled by the formation of the high-energy three-membered cationic intermediate.

Vladimir A. Potapov

Papers

Addition of selenium dibromide to divinyl sulfide: spontaneous rearrangement of 2,6-dibromo-1,4-thiaselenane to 5-bromo-2-bromomethyl-1,3-thiaselenolane

Thia-, Aza-, and Selena[3.3.1]bicyclononane Dichlorides: Rates vs Internal Nucleophile in Anchimeric Assistance

Recent Advances in Organochalcogen Synthesis Based on Reactions of Chalcogen Halides with Alkynes and Alkenes

Reactions of selenium dichloride and dibromide with unsaturated ethers. Annulation of 2,3-dihydro-1,4-oxaselenine to the benzene ring

The reaction of selenium dichloride with divinyl sulfide