The Stereochemistry and Mechanism of The Biosynthesis of Ent-Sandaracopimaradiene and Related Diterpenes

The stereochemistry and mechanism of the cyclization of copalyl pyrophosphate to (+)-sandaracopimaradiene by enzyme extracts from R. cummunis was investigated. (S)-Geranyl-geraniol-1-d was prepared by enzymatic reduction of geranyl-geranial-1-d with horse liver alcohol dehydrogenase and NAD('+) with ethanol as a proton source. Inspection of the vinyl region of the ('1)H NMR spectrum of sandaracopimaradiene biosynthesized from (S)-geranylgeranyl pyrophosphate-1-d indicated that the deuteriovinyl group had the E configuration. The S(,N') cyclization of copalyl pyrophosphate to sandaracopimaradiene therefore proceeds with anti stereochemistry.

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

2014

Author dc:creator

• Drengler, Keith Allan

• Chemistry, Organic

Language dc:language

eng

Identifier

(UMI)AAI8108495

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/67240