טכניון מכון טכנולוגי לישראל
הטכניון מכון טכנולוגי לישראל - בית הספר ללימודי מוסמכים  
M.Sc Thesis
M.Sc StudentRozental Lina
SubjectRemote Functionalization of w-ene Unsaturated Ethers
as a New EVtry to vinyl Metal Species
DepartmentDepartment of Chemistry
Supervisor Professor Ilan Marek
Full Thesis textFull thesis text - English Version


Abstract

A remote functionalization reaction was developed, in which alkenyl ethers with a remote double bond were converted into functionalized skipped dienes in a single reaction sequence. The sequence consisted of a Ru-catalyzed isomerization of the alkenyl ether into a vinyl ether, a zirconation of the crude vinyl ether which made use of the unique property of organozirconium reagents to cleave stable C-O bonds, and of a transmetalation reaction which was followed by the final functionalization step. The reaction proceeded stereoselectively, giving the isomerized double bond exclusively in the (E)-configuration. Allylic electrophiles that were activated by electron-withdrawing substituents gave the highest yields. Finally, the reaction was also performed using a trisubstituted allylic electrophile. The conformation of the obtained product indicated that the final reaction between the vinylmetal species and the electrophile most likely follows a conjugate bimolecular nucleophilic substitution mechanism.