Investigation of the Stereochemistry of the Methyl-to-Methylene Elimination in the Biosynthesis of Several Terpenes Through the Use of Chiral Methyl Labeled Compounds

The synthesis of (R)- (13-$\sp2$H, $\sp3$H) farnesyl diphosphate has been completed by methodology similar to that used for the synthesis of (R)- (9-$\sp2$H, $\sp3$H) geranyl diphosphate. Incubation of the radiolabeled farnesyl diphosphate with 5-epi-aristolochene synthase gave the ($\sp2$H, $\sp3$H) olefin in a 10% radiochemical yield. Analysis by $\sp3$H NMR spectroscopy showed 3 peaks in a 5:1:0.7 ratio which correspond to the (12-$\sp2$H, $\sp3$H) -, (12-$\sp1$H, $\sp3$H) -, and (1-$\sp3$H, 12-$\sp2$H) 5-epi-aristolochene, respectively. However, the assignment of these peaks and the determination of the facial selectivity of the enzyme were not possible owing to the lack of a reference sample of 5-epi-aristolochene for NMR comparisons and NOE experiments.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2015

Author dc:creator

• Elmore, Charles Sherman

Contributors dc:contributor

• Coates, R.M.

• Chemistry, Biochemistry

Language dc:language

eng

Identifier

(MiAaPQ)AAI9812580

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/84376