Which is more likely in trichodiene biosynthesis: hydride or proton transfer?
The mechanisms proposed for enzyme-catalyzed formation of the sesquiterpene natural product trichodiene consistently include a step involving a 1,4-hydride transfer. Using quantum chemical methods (B3LYP/6-31+G(d,p) and mPW1PW91/6-31+G(d,p)), we discovered two alternative pathways for transformation of the intermediate bisabolyl cation to the cuprenyl cation, one of which--a proton-transfer pathway--appears to be much more energetically favorable (by more than 10 kcal/mol) than the hydride transfer pathways usually proposed.
Hong
Young J
YJ
Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, California 95616, USA.
Tantillo
Dean J
DJ
D053138:Cyclohexenes / Q000378:metabolism*; D006859:Hydrogen / Q000737:chemistry; D008958:Models, Molecular; D011522:Protons; D012717:Sesquiterpenes / Q000378:metabolism*
D053138:Cyclohexenes; D011522:Protons; D012717:Sesquiterpenes; C012075:trichodiene; D006859:Hydrogen