The Total Synthesis of (-)-Detoxinine and (+)-Casuarine Using Tandem [4 + 2]/[3 + 2] Nitroalkene Cycloadditions and Cycloadditions of Nitroethylene

The first synthesis of (+)-casuarine, a pentahydroxy pyrrolizidine alkaloid of the alexine/australine subclass, is described. The key step is a tandem inter [4+2]/inter [3+2] nitroalkene cycloaddition involving an oxygenated nitroalkene, chiral vinyl ether, and vinyl silane dipolarophile, which establishes five of the six stereocenters present in this potent glycosidase inhibitor. The completion of the synthesis required only four additional steps to deliver the final product in 20% overall yield.

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

• Hurd, Alexander Ross

Contributors dc:contributor

• Denmark, Scott E.

• Chemistry, Organic

Language dc:language

eng

Identifier

(MiAaPQ)AAI9955629

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/84466