Webthis 1,6-cyclization pathway; although premnaspirodiene 11 may be derived from a different cation intermediate. Clm1-STS cyclizes the same bisabolyl cation intermediate via a different route (blue compounds) primarily to longiborneol 14 with longifolene 2 as an alternative product. Longiborneol becomes the precursor to culmorin 16 and ... WebOct 17, 2007 · Quantum chemical studies on complexes of the 2-norbornyl cation with ammonia and benzene are described. These calculations demonstrate that the delocalized, bridged, nonclassical geometry that is usually favored for this carbocation can be perturbed significantly toward the normally less favorable classical geometry through appropriately …
Exploring biosynthetic diversity with trichodiene synthase
WebSep 8, 2006 · 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 … WebThe biosynthesis of bisabolyl cation from farnesylpyrophosphate invovles five steps: The first step is the removal of pyrophosphate. The se … View the full answer cannot resolve symbol filenameutils
Solved 5 of 6 Problem 16 1-Propose a reasonable biosynthesis
WebApr 15, 2006 · Amino acid alterations in pocket I indicated that early steps of the catalytic process up to the formation of the monocyclic bisabolyl cation are probably localized in this compartment. Mutations in pocket II primarily inhibited the formation of bicylic compounds, suggesting that secondary cyclizations of the bisabolyl cation are catalyzed in ... WebJan 6, 2024 · Second, we identify a sulfur-carbocation dative bonding interaction that anchors the bisabolyl cation in a reactive conformation, avoiding tumbling and premature deprotonation. Specifically, Met73 acts as a chameleon, shifting from an initial sulfur-π interaction in the Michaelis complex to a sulfur-carbocation complex during catalysis. WebSecond, we identify a sulfur-carbocation dative bonding interaction that anchors the bisabolyl cation in a reactive conformation, avoiding tumbling and premature deprotonation. Specifically, Met73 acts as a chameleon, shifting from an initial sulfur-π interaction in the Michaelis complex to a sulfur-carbocation complex during catalysis. fla div of elections