Asymmetric Total Synthesis of (+)-Nominine: Development of a Dual Cycloaddition Strategy for the Synthesis of the Hetisine Alkaloids

A dual cycloaddition strategy for the synthesis of the hetisine alkaloids has been developed and applied to the asymmetric total synthesis of nominine. The approach relies on an early stage intramolecular aza-1,3-dipolar cycloaddition of a 4-oxidoisoquinolinium betaine with an ene-nitrile dipolarophile and a late stage intramolecular [4+2] Diels-Alder cycloaddition. Also of note is the development of a new method for the preparation of 4-oxidoisoquinolinium betaines. Overall, a 16 step asymmetric synthesis of (+)-nominine was accomplished in 1.3% yield, while (+/-)-nominine was prepared in 15 steps in 6.1% yield.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Date dc:date

10000-01-01

Author dc:creator

• Peese, Kevin M.

Contributors dc:contributor

• Gin, David Y.

• Chemistry, Organic

Language dc:language

eng

Identifier

(MiAaPQ)AAI3290348

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/84279