1577-29-3Relevant academic research and scientific papers
Synthesis of the tricyclic core of vinigrol via an intramolecular diels-alder reaction
Grise, Christiane M.,Tessier, Guillaume,Barriault, Louis
, p. 1545 - 1548 (2008/02/02)
Equation presented Herein, we present a successful synthesis of the tricyclic core of vinigrol (1). Our approach takes advantage of a highly regioselective intramolecular Diels-Alder reaction of the diene 11 to construct two rings of the tricyclic vinigro
Inhibitors of Thermus thermophilus isopropylmalate dehydrogenase
Pirrung,Han,Ludwig
, p. 2430 - 2436 (2007/10/02)
In an attempt to use mechanism-based design for the discovery of inhibitors of the isopropylmalate dehydrogenase from T. thermophilus, we have prepared and studied a number of potential mimics for an intermediate in the oxidative decarboxylation of isopropyl malate, the enol or enolate of α-ketoisocaproate. Because hydroxamate and dicarboxylate enolate mimics are strong, uncompetitive inhibitors of the enzyme and vinyl fluoride enol mimics are weak, competitive inhibitors, it is suggested that the reaction involves the enolate. The uncompetitive inhibition by a number of anionic compounds suggests, in combination with previous studies in other laboratories, that they mimic the enolate product of the decarboxylation. An explanation for the potency of the inhibition of IMDH by these compounds is proposed based on the electrostatic interaction of product and cofactor.
Formation of α-iminoketones and α-diimines versus Favorskii rearrangement products from the reaction of α,α′-dibromoketones and primary amines
De Kimpe, Norbert,D'Hondt, Luc,Mones, Luc
, p. 3183 - 3208 (2007/10/02)
The reaction of aliphatic acyclic α,α'-dibromoketones with primary amines gave rise to α-iminoketones and α-diimines. Both reaction products could be selectively obtained under appropriate reaction conditions. Sterically hindered α,α-dibromoketones did no
Remote Control of Stereogenicity Transfer by Ring-Generated Anisotropic Orbital Overlap. Stereochemistry of Hydrogen Shift in the Intramolecular Reverse Ene Reaction of a cis-2- Alkyl-1 -alkenylcyclopropane
Parziale, Patti A.,Berson, Jerome A.
, p. 4595 - 4606 (2007/10/02)
The thermal rearrangement of cis-2-(2-propyl)-1(E)-propenylcyclopropane at temperatures near 230 °C in the gas phase occurs with activation parameters of Ea = 35.5 ±0.6 kcal/mol and log A = 12.05 ±0.5 (A, s-1). The optically active isotopically doubly labeled analogue (cis-2(S)-(2(S)-propyl-1-d3)-1(S)-(1(E)-propenyl-2-rf)cyclopropane 5 was synthesized in 12 steps from dicyciopentadiene. Pyrolysis of 5 gave only 2-methyl-octa-2(Z),5(Z)-diene-1-d3-7(S)-d, with high stereospecificity at each of the three sites of stereogenicity. This result is the one predicted if the reaction is controlled by optimal overlap ' of the reacting C-H and π bond orbitals with the Cs symmetric component of the degenerate 3E' highest occupied orbital of the cyclopropane ring.
