Solvolytic enolization of scytalone.
[reaction--see text] The major conformation of scytalone has an envelope shape with C3 forming the flap and the C3 hydroxyl in the equatorial position as determined by quantum mechanical calculations and corroborated by NMR. The C2 axial pro-R is slower to exchange with solvent than the equatorial pro-S hydrogen. Modeling the transition state for enolate formation points to a deprotonation through the flipped envelope conformation in which the C3-hydroxyl and the C2 pro-S hydrogen are axial.
Basarab
G S
GS
E. I. DuPont de Nemours Central Research and Development, Wilmington, Delaware 19880-0328, USA. gregory.s.basarab@usa.dupont.com
Jordan
D B
DB
Zheng
Y J
YJ
D000935:Antifungal Agents / Q000737:chemistry / Q000378:metabolism; D001665:Binding Sites; D002384:Catalysis; D004791:Enzyme Inhibitors / Q000737:chemistry / Q000378:metabolism; D006836:Hydro-Lyases / Q000037:antagonists & inhibitors; D008968:Molecular Conformation; D009284:Naphthols / Q000737:chemistry* / Q000378:metabolism; D019906:Nuclear Magnetic Resonance, Biomolecular; D012997:Solvents / Q000378:metabolism; D013816:Thermodynamics; D014867:Water / Q000378:metabolism
D000935:Antifungal Agents; D004791:Enzyme Inhibitors; D009284:Naphthols; D012997:Solvents; D014867:Water; C012547:scytolone; D006836:Hydro-Lyases; C082741:scytalone dehydratase