Mechanistic investigation of the base-promoted cycloselenoetherification of pent-4-en-1-ol.
The mechanism of phenylselenoetherification of pent-4-en-1-ol using some bases (pyridine, triethylamine, quinoline, 2,2'-bipyridine) as catalyst was examined through studies of kinetics of the cyclization, by UV-VIS spectrophotometry. It was demonstrated that the intramolecular cyclization is facilitated in the presence of bases caused by the hydrogen bond between base and alkenol's OH-group. The obtained values for rate constants have shown that the reaction with triethylamine is the fastest one. Quantum chemical calculations (MP2(fc)/6-311+G**//B3LYP/6-311+G**) show, that the transition state of the cyclisation is S(N)2 like.
Rvovic
Marina D
MD
Faculty of Science, Department of Chemistry, University of Kragujevac, Kragujevac, Serbia.
Divac
Vera M
VM
Puchta
Ralph
R
Bugarčić
Zorica M
ZM
D002384:Catalysis; D003500:Cyclization; D005021:Ethylamines / Q000737:chemistry*; D006860:Hydrogen Bonding; D007700:Kinetics; D008958:Models, Molecular; D008968:Molecular Conformation; D016566:Organoselenium Compounds / Q000737:chemistry*; D000439:Pentanols / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*; D011804:Quinolines / Q000737:chemistry*
D005021:Ethylamines; D016566:Organoselenium Compounds; D000439:Pentanols; D011725:Pyridines; D011804:Quinolines; C561023:pent-4-en-1-ol; C037219:quinoline; C016162:triethylamine