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61.
TpMo(CO)2(5-alkenyl-eta-2,3,4-pyranyl) diene complexes function as excellent chiral scaffolds for the efficient regio- and enantiocontrolled synthesis of highly functionalized 1-oxadecaline derivatives through a novel transition metal-mediated Diels-Alder reaction. Very good to excellent yields and excellent levels of endo selectivity are obtained, and the reaction gives products with complete retention of enantiomeric purity when carried out with chiral, nonracemic scaffolds. A subtle structural modification on the diene (replacement of an H by a trans-CH3 group) leads to a complete change of regiochemistry, which is discussed from a mechanistic point of view. The role of the eta3-coordinated TpMo(CO)2 moiety is also critical to the further functionalization of the [4 + 2] cycloadducts, as illustrated by the preparation of 20 variously functionalized 1-oxadecaline derivatives (>98% ee when carried out with high enantiopurity scaffolds). 相似文献
62.
Carboranyl aldehydes react with alpha,beta-unsaturated esters, ketones, and nitriles in the presence of DABCO to provide functionalized carboranyl alcohols in good yields. Acetates of these alcohols undergo a facile isomerization with a variety of nucleophiles and afford structurally interesting carboranes. Biological evaluation of these molecules exhibited impressive antiproliferative activity for brain and breast cancer cells. 相似文献
63.
Ramón Valencia Antonio Rodríguez‐Fortea Dr. Anna Clotet Dr. Coen de Graaf Dr. Manuel N. Chaur Luis Echegoyen Prof. Dr. Josep M. Poblet Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(41):10997-11009
An extensive study of the redox properties of metal nitride endohedral fullerenes (MNEFs) based on DFT computational calculations has been performed. The electronic structure of the singly oxidized and reduced MNEFs has been thoroughly analyzed and the first anodic and cathodic potentials, as well as the electrochemical gaps, have been predicted for a large number of M3N@C2n systems (M=Sc, Y, La, and Gd; 2n=80, 84, 88, 92, and 96). In particular, calculations that include thermal and entropic effects correctly predict the different anodic behavior of the two isomers (Ih and D5h) of Sc3N@C80, which is the basis for their electrochemical separation. Important differences were found in the electronic structure of reduced M3N@C80 when M=Sc or when M is a more electropositive metal, such as Y or Gd. Moreover, the changes in the electrochemical gaps within the Gd3N@C2n series (2n=80, 84, and 88) have been rationalized and the use of Y‐based computational models to study the Gd‐based systems has been justified. The redox properties of the largest MNEFs characterized so far, La3N@C2n (2n=92 and 96), were also correctly predicted. Finally, the quality of these predictions and their usefulness in distinguishing the carbon cages for MNEFs with unknown structures is discussed. 相似文献
64.
Almodóvar I Ramírez-Rodríguez O Barriga A Rezende MC Araya-Maturana R 《Rapid communications in mass spectrometry : RCM》2011,25(2):370-378
The fragmentation patterns of nine di-, tri- and tetracyclic hydroquinones with potential antitumor activity were rationalized by invoking competing mechanisms that included sterically accelerated homolytic cleavage, Meerwein-type rearrangements and dehydrations through elimination or intramolecular nucleophilic substitution. 相似文献
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