Efficient construction of the oxatricyclo[6.3.1.0(0,0)]dodecane core of komaroviquinone using a cyclization/cycloaddition cascade of a rhodium carbenoid intermediate.
The rhodium(II)-catalyzed cyclization/cycloaddition cascade of a o-carbomethoxyaryl diazo dione is described as a potential route to the oxatricyclo[6.3.1.0(0,0)]dodecane substructure of the icetexane diterpene komaroviquinone. The initially formed carbonyl ylide dipole prefers to cyclize to an epoxide at 25 degrees C but can be induced to undergo cycloaddition across the tethered pi-bond at higher temperatures. [reaction: see text]
Padwa
Albert
A
Department of Chemistry, Emory University, Atlanta, GA 30322, USA. chemap@emory.edu
Boonsombat
Jutatip
J
Rashatasakhon
Paitoon
P
Willis
Jerremey
J
D000473:Alkanes / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D004224:Diterpenes / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D011809:Quinones / Q000138:chemical synthesis* / Q000737:chemistry; D012238:Rhodium / Q000737:chemistry; D013696:Temperature
D000473:Alkanes; D004224:Diterpenes; D011809:Quinones; C508550:komaroviquinone; D012238:Rhodium