Portal de Periódicos da CAPES

A Computational Study of Radical Haloacetal Cyclizations Controlled by the Acetal Center

2003; Wiley; Volume: 9; Issue: 7 Linguagem: Inglês

10.1002/chem.200390181

1521-3765

Olivier Corminboeuf, Philippe Renaud, Carl H. Schiesser,

Catalytic C–H Functionalization Methods

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.