Lancifodilactone G: insights about an unusually stable enol.
From quantum mechanics calculations we confirm that the naturally occurring enol lancifodilactone G is stable over the keto form (by 2.6 kcal/mol in water), the only known stable aliphatic enol (devoid of conjugated or bulky aromatics and lacking a 1,3-diketone structural motif known to stabilize enols). We determine architectural elements responsible for the enol stabilization and find a mechanism for keto-enol conversion in solution. In addition, we correct previously reported computational results that were performed on the misinterpreted structure demonstrating that the enol form of this natural product is more stable than previously thought.
Chenoweth
David M
DM
Materials and Process Simulation Center, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
Chenoweth
Kimberly
K
Goddard
William A
WA
D000438:Alcohols / Q000737:chemistry*; D000465:Algorithms; D001688:Biological Products / Q000737:chemistry*; D006860:Hydrogen Bonding; D007700:Kinetics; D011789:Quantum Theory; D013237:Stereoisomerism; D013816:Thermodynamics; D014315:Triterpenes / Q000737:chemistry*; D014867:Water / Q000737:chemistry
D000438:Alcohols; D001688:Biological Products; D014315:Triterpenes; C507939:lancifodilactone G; D014867:Water