Computational studies of the tropone natural products, thiotropocin, tropodithietic acid, and troposulfenin. Significance of thiocarbonyl-enol tautomerism.
Computations provide insight to the stability and isomeric possibilities of thiotropocin, tropodithietic acid, and troposulfenin. Thiotropocin and tropodithietic acid contain a flat 7-membered ring and delocalized pi-bonds similar to those of tropylium ion (C(7)H(7)(+)). Troposulfenin is far less stable; it contains a puckered tropone ring and localized bonds similar to 1,3,5-cycloheptatriene. A facile 1,5-hydrogen shift suggests that thiotropocin and tropodithietic acid exist as a pair of interconverting tautomers. Loss of an acidic proton from these three tautomers produces the same conjugate base structure.
Greer
Edyta M
EM
Department of Chemistry and Graduate Center & The City University of New York, Brooklyn College, Brooklyn, New York 11210, USA.
Aebisher
David
D
Greer
Alexander
A
Bentley
Ronald
R
D001685:Biological Factors / Q000737:chemistry*; D003198:Computer Simulation; D004987:Ethers / Q000737:chemistry*; D008956:Models, Chemical; D008968:Molecular Conformation; D011789:Quantum Theory; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000737:chemistry; D014334:Tropolone / Q000031:analogs & derivatives* / Q000737:chemistry*
D001685:Biological Factors; D004987:Ethers; D013438:Sulfhydryl Compounds; C527336:tropodithietic acid; D014334:Tropolone; C043269:thiotropocin