125642-76-4Relevant articles and documents
Carbenes and the O-H bond: Bicycloalkylidenes
Kirmse, Wolfgang,Meinert, Thomas,Modarelli, David A.,Platz, Matthew S.
, p. 8918 - 8927 (2007/10/02)
Photolyses of spirobicyclic diazirines in alcohols have been investigated in order to elucidate the insertion reactions of bicycloalkylidenes with O-H bonds. The formation of ethers from norbornane-derived diazirines (16 and 30) was traced to the intervention of diazo compounds which react by way of diazonium ions. Scavenging of the diazo compounds with potent dipolarophiles led to almost exclusive formation of nortricyclenes from 2-norbornylidenes (17 and 32). In contrast, 2-bieyclo[2,1.1]hexylidene (45) was found to undergo intermolecular reactions, including addition to alkenes and C-H insertion with cycloalkanes. When alcoholic solutions of bicyclo[2.1.1]hexane-derived diazirines (41, 58, 73, and 76) were irradiated, diazo scavengers did not eliminate the formation of ethers. By means of deuterium labels or methyl groups, rearrangement and fragmentation reactions were detected that are characteristic of carbocations (ion pairs). Protonation of 2-bicyclo[2.1.1]hexylidenes by ROH is therefore implied. Laser flash photolysis studies confirmed the divergent lifetimes of 17 (0.1 ns) and 45 (50-600 ns). The reaction rate of 45 was found to increase with the acidity of the alcohols.
The Influence of Intramolecular Dynamics on Branching Ratios in Thermal Rearrangements
Newmann-Evans, Richard H.,Simon, Reyna J.,Carpenter, B. K.
, p. 695 - 711 (2007/10/02)
1- and 2-phenylbicyclohex-2-enes-5-d undergo thermal rearrangement to give products, differing only in the location of the deuterium, in ratio of about 9:1, but with identical activation enthalphies.Similarly, opticallly active trans-2-methyl-1-(trans-2-phenylethenyl)cyclopropane is found to rearrange to enantiomeric methylphenylcyclopentenes that are formed in a 5.9:1 ratio but with virtually identicyl activation enthalphies.Barring repeated coincidence, these results do not seem to be explicable within the framework of statistical theories of unimolecular kinetics such as RRKM theory, transition state theory, and variational transition state theory.The possible influence of dynamic effects in these and other unimolecular reactions is discussed.