Highly selective Diels-Alder reactions of dienophiles with 1, 3-cyclohexadiene mediated by Yb(OTf)(3).2H(2)O and ultrahigh pressures.
[reaction: see text] Ultrahigh pressures and catalytic Yb(OTf)(3).2H(2)O were found to mediate Diels-Alder reactions of various electron-deficient dienophiles with 1,3-cyclohexadiene to produce endo-bicyclo[2.2. 2]oct-2-enes in moderate to excellent yield and selectivity. The proposed total synthesis of hapalindole Q based on bicyclo[2.2. 2]oct-2-ene construction by Diels-Alder reaction and subsequent olefin cleavage is outlined. Preliminary results demonstrating the viability of this strategy are presented.
Kinsman
A C
AC
Department of Chemistry, University of Western Ontario, London, Ontario N6A 5B7, Canada.
Kerr
M A
MA
D000470:Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D001643:Bridged Bicyclo Compounds / Q000737:chemistry*; D003510:Cyclohexanes / Q000737:chemistry*; D053138:Cyclohexenes; D015195:Drug Design; D007211:Indoles / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D011312:Pressure; D013329:Structure-Activity Relationship
D000470:Alkaloids; D001643:Bridged Bicyclo Compounds; D003510:Cyclohexanes; D053138:Cyclohexenes; D007211:Indoles; C034005:1,3-cyclohexadiene