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. 2012 Jul 18;134(28):11369-71.
doi: 10.1021/ja3043245. Epub 2012 Jul 9.

Effect of isotopically sensitive branching on product distribution for pentalenene synthase: support for a mechanism predicted by quantum chemistry

Liansuo Zu  1 , Meimei Xu, Michael W Lodewyk, David E Cane, Reuben J Peters, Dean J Tantillo
Affiliations

Effect of isotopically sensitive branching on product distribution for pentalenene synthase: support for a mechanism predicted by quantum chemistry

Liansuo Zu et al. J Am Chem Soc. .

Abstract

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.

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Figures

Figure 1
Figure 1
Effect of deuteration at C-6 of FPP on the ratio of products generated by H308A pentalenene synthase. GC-MS chromatograms of reaction mixture from either unlabeled FPP (top) or [6-2H]-FPP (bottom); * indicates β-elemene from Cope rearrangement of germacrene A.
Scheme 1
Scheme 1
Three mechanisms proposed for the formation of pentalenene (1) and Δ6-protoilludene (2) from (E,E)-farnesyl diphosphate.
See this image and copyright information in PMC

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