697 research outputs found
Hydrogen adsorption on and desorption from Si: Considerations on the applicability of detailed balance
The translational energy of D2 desorbed from Si(100) and Si(111) surfaces was measured and found roughly equal to the thermal expectation at the surface temperature Ts. Combining these results with previously measured internal state distributions, the total energy of the desorbed molecules is approximately equal to the equilibrium expectation at Ts. Thus adsorption experiments, which suggest a large energetic barrier, are at variance with desorption experiments, which exhibit a trivial adsorption barrier, and the applicability of detailed balance for this system needs to be reexamined
An alternative synthetic access to cis-4a-Methyloctahydrophenanthrene, a biomarker of Sergipe-Alagoas Basin petroleum in Brazil
cis-4a-Methyloctahydrophenanthrene (1) was prepared in 8 steps (23% overall yield) from 2-bromophenyl)acetic acid (3) and cyclohexane-1,3-dione (6). A highly cis-diastereoselective Michael-type Heck coupling served as the key step in the assembly of the tricyclic skeleton. This compound 1 was used as gas chromatography standard which allowed the unequivocal identification of a minor biomarker present in Carmopolis oil from the Sergipe-Alagoas Basin in Brazil.13566466
Au-catalyzed biaryl coupling to generate 5- to 9-membered rings: turnover-limiting reductive elimination versus π-complexation
The intramolecular gold–catalyzed arylation of arenes by aryltrimethylsilanes has been investigated from both a mechanistic and preparative aspect. The reaction generates five to nine membered rings, and of the 44 examples studied, ten include a heteroatom (N, O). The tethering of the arene to the arylsilane not only provides a tool to probe the impact of the conforma-tional flexibility of Ar–Au–Ar intermediates, via systematic modulation of the length of aryl-aryl linkage, but also the ability to arylate neutral and electron-poor arenes - substrates that do not react at all in the intermolecular process. Rendering the arylation intramolecular also results in phenomenologically simpler reaction kinetics, and overall these features have facili-tated a detailed study of linear free energy relationships, kinetic isotope effects, and the first quantitative experimental data on the effects of aryl electron-demand and conformational freedom on the rate of reductive elimination from diaryl gold(III) species. The turnover-limiting step for the formation of a series of fluorene derivatives is sensitive to the electronics of the arene and changes from reductive elimination to π-complexation for arenes bearing strongly electron-withdrawing substitu-ents (σ >0.43). Reductive elimination is accelerated by electron-donating substituents (□ = -2.0) on one or both rings, with the individual σ-values being additive in nature. Longer and more flexible tethers between the two aryl rings results in faster reductive elimination from Ar-Au(X)-Ar, and to the π-complexation of the arene by Ar-AuX2 becoming the turnover-limiting step
New GM1 ganglioside derivatives for selective single and double labelling of the natural glycosphingolipid skeleton.
Ru-Catalyzed C-H Arylation of Fluoroarenes with Aryl Halides
We gratefully acknowledge the Engineering and Physical
Sciences Research Council (EPSRC, EP/I038578/1 and EP/
K039547/1) for funding and the European Research Council
for a Starting Grant (to I.L.).
Limitations in determining enantiomeric excess of alcohols by 31P-NMR of the phosphonate derivatives
The use of diastereomeric alcohol dialkylphosphonate derivatives to determine the enantiomeric excesses via 31P-NMR signal ratios of anisochronous meso and threo isomers was successfully applied to secondary alcohols (Feringa s method). Expansion of the methodology to primary alcohols possessing the hydroxyl groups thethered to the stereogenic centers by two or more methylene groups proved the method to be inefficent. The comparison between the coupled and decoupled spectra is important in order to identify the signals corresponding to the dialkylphosphonates. Nevertheless the methodology should be applied whenever the amount of the alcohol and its structure are not the limiting factors.O uso de derivados fosfonatos de dialquila diastereoisoméricos na determinação de excessos enantioméricos através da razão entre os sinais de 31P-NMR anisócronos dos isômeros meso e treo, foi bem sucedido para álcoois secundários (método de Feringa), porém revelou-se ineficiente para álcoois primários com dois ou mais grupos metilênicos entre as hidroxilas e os centros estereogênicos. Observou-se adicicionalmente que era importante obter os espectros acoplados e desacoplados para se certificar dos picos correspondentes aos fosfonatos de dialquila. Entretanto, esta metodologia merece ser aplicada sempre que a quantidade de álcool disponÃvel e sua estrutura não forem fatores limitantes.293298Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento CientÃfico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de NÃvel Superior (CAPES
Nickel-Catalyzed Carbon–Carbon Bond-Forming Reactions of Unactivated Tertiary Alkyl Halides: Suzuki Arylations
The first Suzuki cross-couplings of unactivated tertiary alkyl electrophiles are described. The method employs a readily accessible catalyst (NiBr[subscript 2]·diglyme/4,4′-di-tert-butyl-2,2′-bipyridine, both commercially available) and represents the initial example of the use of a group 10 catalyst to cross-couple unactivated tertiary electrophiles to form C–C bonds. This approach to the synthesis of all-carbon quaternary carbon centers does not suffer from isomerization of the alkyl group, in contrast with the umpolung strategy for this bond construction (cross-coupling of a tertiary alkylmetal with an aryl electrophile). Preliminary mechanistic studies are consistent with the generation of a radical intermediate along the reaction pathway.National Institute of General Medical Sciences (U.S.) (R01-GM62871)Merck Research Laboratories (Summer Fellowship
A Selective Intramolecular 5-exo-dig or 6-endo-dig Cyclization en Route to 2-Furanone or 2-Pyrone Containing Tricyclic Scaffolds
Direct C(sp2)-H chlorination of ketene dithioacetals using FeCl3 as the chloride source and PhI(OAc)2 as an oxidant
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