85807-79-0Relevant articles and documents
Dihalocarbene insertion reactions into C-H bonds of compounds containing small rings: Mechanisms and regio- and stereoselectivities
Brinker, Udo H.,Lin, Guoying,Xu, Linxiao,Smith, William B.,Mieusset, Jean-Luc
, p. 8434 - 8451 (2008/02/13)
(Chemical Equation Presented) Novel insertion reactions of dichloro- and dibromocarbene into carbon-hydrogen bonds adjacent to cyclopropane rings are reported. It is found that the predominant isomers formed in the reactions with bicyclo[4.1.0]heptane result from insertion into the endo carbon-hydrogen bonds alpha to the three-membered ring. In the reactions of bicyclo[3.1.0]hexane, however, the exo dihalocarbene insertion products are formed as the major isomers. In some compounds cyclopropane rings "activate" adjacent carbon-hydrogen bonds, whereas other systems containing three-membered rings do not. Moreover, the influence of various substituents (methyl, geminal dimethyl, phenyl, methoxy, and ethoxy) attached to bicyclo-[3.1.0]hexane and bicyclo[4.1.0]heptane in dihalocarbene reactions has been studied. The findings can be explained by the concept of maximum orbital overlaps of Walsh orbitals of the cyclopropane rings and the α carbon-hydrogen bonds. In stark contrast, selective insertion into the tertiary carbon-hydrogen bonds of the cyclobutane ring in bicyclo[4.2.0]octane is observed.
Stoichiometric Reactions of Nonconjugated Dienes with Zirconocene Derivatives. Further Delineation of the Scope of Bicyclization and Observation of Novel Multipositional Alkene Regioisomerization
Negishi, Ei-ichi,Maye, John P.,Chouery, Daniele
, p. 4447 - 4462 (2007/10/02)
The reaction of n-Bu2ZrCp2 with nonconjugated dienes containing substituted vinyl groups can lead to either bicyclization or the formation of conjugated diene-zirconocenes via multipositional regioisomerization.
ZIRCONOCENE-PROMOTED STEREOSELECTIVE BICYCLIZATION OF 1,6- AND 1,7-DIENES TO PRODUCE TRANS-ZIRCONABICYCLOOCTANES AND CIS-ZIRCONABICYCLONONANES.
Rousset, Christophe J.,Swanson, Douglas R.,Lamaty, Frederic,Negishi, Ei-ichi
, p. 5105 - 5108 (2007/10/02)
The Zr-promoted bicyclization of 1,6- and 1,7-dienes can stereoselectively produce trans-zirconabicyclooctanes and cis-zirconabicyclononanes, respectively; these compounds can be readily converted into protonolysis, halogenolysis, and carbonylation products.
