Why a proximity-induced Diels-Alder reaction is so fast.
Unlike normal Diels-Alder reactions of acyclic alkadienes with alkenes, the vinylbicyclo[2.2.2]octene employed in the Baran total synthesis of vinigrol undergoes a quantitative Diels-Alder reaction with a tethered alkene at room temperature. Density functional theory calculations reveal that this unprecedented reactivity originates from a combination of preorganization, diene strain, and tether stabilization.
School of Chemistry, University of Melbourne, and Australian Research Council Centre of Excellence for Free Radical Chemistry and Biotechnology, VIC 3010, Australia. ekrenske@unimelb.edu.au
Elizabeth H
EH
Krenske
Emma W
EW
Perry
Steven V
SV
Jerome
Thomas J
TJ
Maimone
Phil S
PS
Baran
K N
KN
Houk
D003500:Cyclization; D004224:Diterpenes / Q000138:chemical synthesis*; D008958:Models, Molecular; D015394:Molecular Structure; D013997:Time Factors
D004224:Diterpenes; C055112:vinigrol