A computational study of radical haloacetal cyclizations controlled by the acetal center.
The stereochemical outcome of the radical haloacetal cyclization reaction (Ueno-Stork reaction) has been examined by ab initio and other molecular orbital techniques. It was found that the stereochemistry of 5-exo- and 6-exo trig cyclizations can be accurately predicted from calculations using moderate levels of theory (UHF/6-311G** or B3LYP/6-311G**). A simplified computational procedure, easily run on a standard desktop computer, has been developed that provides excellent predictive ability for the stereochemical outcome for the reactions in question. Interestingly, a novel twist transition state has been identified for the first time in 5-exo-trig radical cyclization reactions.
Corminboeuf
Olivier
O
Department of Chemistry and Biochemistry, University of Bern Freiestrasse 3, Switzerland.
Renaud
Philippe
P
Schiesser
Carl H
CH