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

Elmore, Charles Sherman

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Description

Title

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

Author(s)

Elmore, Charles Sherman

Issue Date

1997

Doctoral Committee Chair(s)

Coates, R.M.

Department of Study

Chemistry

Discipline

Chemistry

Degree Granting Institution

University of Illinois at Urbana-Champaign

Degree Name

Ph.D.

Degree Level

Dissertation

Keyword(s)

Chemistry, Biochemistry

Language

eng

Abstract

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.

Graduation Semester

1997

Type of Resource

text

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