Effect of isotopically sensitive branching on product distribution for pentalenene synthase: support for a mechanism predicted by quantum chemistry.
Mechanistic proposals for the carbocation cascade reaction leading to the tricyclic sesquiterpene pentalenene are assessed in light of the results of isotopically sensitive branching experiments with the H309A mutant of pentalenene synthase. These experimental results support a mechanism for pentalenene formation involving a 7-protoilludyl cation whose intermediacy was first predicted using quantum-chemical calculations.
Department of Chemistry, University of California, Davis, California 95616, USA.
Liansuo
L
Zu
Meimei
M
Xu
Michael W
MW
Lodewyk
David E
DE
Cane
Reuben J
RJ
Peters
Dean J
DJ
Tantillo
D002412:Cations; D019753:Intramolecular Lyases / Q000737:chemistry*; D009154:Mutation; D011789:Quantum Theory
D002412:Cations; D019753:Intramolecular Lyases; C048278:farnesylpyrophosphate cyclase