Computational study of solvation and stereoselectivity in deprotonation of cyclohexene oxide by a chiral lithium amide
1999; Elsevier BV; Volume: 10; Issue: 2 Linguagem: Inglês
10.1016/s0957-4166(98)00501-1
ISSN1362-511X
AutoresSten O. Nilsson Lill, Per I. Arvidsson, Per Ahlberg,
Tópico(s)Chemical Reaction Mechanisms
ResumoA detailed computational investigation of possible activated complexes in the epoxide opening of cyclohexene oxide by a chiral lithium amide is presented. Transition states for the two routes giving (S)- and (R)-alkoxides with and without solvent have been calculated. Geometry optimizations at PM3 and HF/3-21G levels of theory, and single point calculations at B3LYP/6-31+G(d) level have been used. The experimentally obtained stereoselectivity is semi-quantitatively reproduced at all levels except PM3//PM3. The factors found to control the stereoselectivity are solvation and some non-bonded interactions other than those previously proposed.
Referência(s)