Supramolecular Catalysis of a Unimolecular Transformation: Aza-Cope Rearrangement within a Self-Assembled Host

Supramolecular catalysis of a unimolecular transformation: aza-Cope rearrangement within a self-assembled host.

Chemists have long envied the ability of enzymes to manipulate reaction energetics and specificity through steric confinement and precise functional-group interactions. The enormous rate accelerations that enzymes achieve at modest temperatures may be attributed to their high degree of complexity, and the synthetic chemist is hard pressed to create such well-constructed catalytic scaffolds. Yet...

A Theoretical Investigation of Kinetics and Mechanism of Aza-Cope Rearrangement

A theoretical study of the kinetic and mechanism of 3-aug-Cope rearrangement in gas phase was performed usingDET methods at B3LYP levels of theory with 6-3114iG(d,p) bass set at 298.I5K. Equilibrium moleculargeometries and harmonic vibrational frequencies of the reactant, transition state Did product were calculated. Then,rate constant and activation thermodynamics parameters were calculated an...

a theoretical investigation of kinetics and mechanism of aza-cope rearrangement

a theoretical study of the kinetic and mechanism of 3-aug-cope rearrangement in gas phase was performed usingdet methods at b3lyp levels of theory with 6-3114ig(d,p) bass set at 298.i5k. equilibrium moleculargeometries and harmonic vibrational frequencies of the reactant, transition state did product were calculated. then,rate constant and activation thermodynamics parameters were calculated an...

Transformation of Soybean Oil to Various Self- Assembled Supramolecular Structures

A double intramolecular cage contraction within a self-assembled metallo-supramolecular bowl.

When isolated in the high vacuum of an ESI-FTICR mass spectrometer, bowl-shaped metallo-supramolecular M(6)L(4) assemblies undergo a surprising and mechanistically interesting intramolecular double cage contraction to yield smaller M(3)L(2) cages.