Tandem Cycloaddition Chemistry of Nitroalkenes: Total Synthesis of (+)-1-Epiaustraline and Synthesis of the Pentacyclic Core of (+/-)-Scandine

The successful synthesis of the (+)-scandine core began with a tandem conjugate addition/ [3+2] nitronate cycloaddition. This approach proceeded with high chemical yield and modest diastereoselectivity to provide an advanced bicyclic intermediate. Construction of two of the remaining three rings was accomplished by an intramolecular Heck cyclization of a pendant aryl iodide. This process proceeded with high diastereoselectivity to build vicinal quaternary centers. The final ring was created by reductive amination of a pyrrolidine aldehyde. This synthesis provided the core structure of (+/-)-scandine in 16 steps and 4.8% overall yield from 2,4-pentadienyl dimethyl malonate.

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

• Cottell, Jeromy John

Contributors dc:contributor

• Denmark, Scott E.

• Chemistry, Organic

Language dc:language

eng

Identifier

(MiAaPQ)AAI3153278

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/84148