Origin of enantioselection in Hetero-Diels-Alder reactions catalyzed by naphthyl-TADDOL.
The asymmetric hetero-Diels-Alder reaction of benzaldehyde with 1-dimethylamino-3- tert-butyldimethylsiloxy butadiene catalyzed by ( R, R)-1-Np-TADDOL was studied using computational methods. A theoretical rationale was developed through the combined use of molecular mechanics and ONIOM(B3LYP/6-31G(d):AM1) calculations. The origins of stereoselection in this process were identified, and excellent correlation between experiment and theory was found.
Anderson
Christopher D
CD
Department of Chemistry and Biochemistry,University of California, Los Angeles, California 90095-1569, USA.
Dudding
Travis
T
Gordillo
Ruth
R
Houk
K N
KN
D000447:Aldehydes / Q000737:chemistry; D002384:Catalysis; D004148:Dioxolanes / Q000737:chemistry*; D000432:Methanol / Q000031:analogs & derivatives* / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D009281:Naphthalenes / Q000737:chemistry*; D013237:Stereoisomerism
D000447:Aldehydes; D004148:Dioxolanes; D009281:Naphthalenes; C516101:alpha,alpha,alpha',alpha'-tetraaryl-1,3-dioxolane-4,5-dimethanol; C531273:naphthyl-TADDOL; D000432:Methanol