A promiscuous proton in taxadiene biosynthesis?
Herein we describe quantum chemical calculations on a two-step proton-transfer pathway that interconverts key intermediates in the biosynthesis of taxa-4,11-diene, a precursor of Taxol, that provides an energetically more favorable alternative to the usually proposed direct proton-transfer pathway. In effect, the bicyclic diterpene skeleton involved in this rearrangement provides a cage of three pi-bonds that surrounds a locally mobile proton. [reaction: see text]
Gutta
Pradeep
P
Department of Chemistry, University of California-Davis, One Shields Avenue, Davis, CA 95616, USA.
Tantillo
Dean J
DJ
D000465:Algorithms; D000475:Alkenes / Q000378:metabolism*; D004224:Diterpenes / Q000378:metabolism*; D015394:Molecular Structure; D011522:Protons; D011789:Quantum Theory; D013816:Thermodynamics
D000475:Alkenes; D004224:Diterpenes; D011522:Protons; C093125:taxa-4(5),11(12)diene