Ring size effects

Quantum mechanical/molecular mechanical study on the Favorskii rearrangement in aqueous media has been carried out.39 The results obtained by QM/MM methods show that, of the two accepted mechanisms for Favorskii rearrangement, the semibenzilic acid mechanism (a) is favored over the cyclopropanone mechanism (b) for the a-chlorocyclobutanone system (Scheme 6.2). However, the study of the ring-size effects reveals that the cyclopropanone mechanism is the energetically preferred reactive channel for the a-chlorocyclohexanone ring, probably due to the straining effects on bicycle cyclopropanone, an intermediate that does not appear on the semibenzilic acid pathway. These results provide new information on the key factors responsible for the behavior of reactant systems embedded in aqueous media. 

The chromium-catalyzed coupling is extended to the intramolecular cycli-zation to the dials 43. The O-chelating silyl scavenger is used to control the stereoselectivity as shown in Scheme 25 [61,62]. The ring size effect on the stereoselectivity is also investigated. 

As previously pointed out in the discussion of ring size effects on bond homolyses the largest steric acceleration by bulky substituents is expected for the thermal cleavage of C-C-bonds in tetra- or hexasubstituted ethanes 26. Im comparison to azoal-... 

Although these findings had seemed to resolve the conflicting situations, Nickon and coworker 57) reported an interesting ring-size effect directing the course of this acidic isomerization. 

J-Bonded metal complexes, hydrodesulfurization models with benzothiophene, 1, 769 with dibenzothiophene, 1, 769 Bonding studies energetics, 1, 285 overview, 1, 573—603 ring size effects, 1, 396 strength, 1, 609... 

---