Development of a Diastereoselective [4+2]-Annulation of Vinyl Carbodiimides With Chiral N-Alkyl Imines and Its Application to the Synthesis of the Batzelladine Alkaloids: Total Synthesis of (+)-Batzelladine a and (-)-Batzelladine D

A diastereoselective [4+2] annulation of vinyl carbodiimides with chiral N-alkyl imines has been developed to access the stereochemically rich anti-fused polycyclic guanidine cores of the batzelladine alkaloids. Application of this strategy, together with additional key steps such as a long-range directed hydrogenation and a diastereoselective intramolecular iodoamination, led to highly convergent total syntheses of (-)-batzelladine D and (+)-batzelladine A with excellent stereocontrol. Overall, a 13 step asymmetric synthesis of -(-)batzelladine D was accomplished in 7.4% yield, and a 20 step asymmetric synthesis of (+)-batzelladine A was completed in 2.0% yield. Investigations into the application of the imine/vinyl carbodiimide [4+2]-annulation to the syn-fused tricyclic guanidine cores of the batzelladines are also described.

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

• Arnold, Michael A.

Contributors dc:contributor

• Gin, David Y.

• Chemistry, Organic

Language dc:language

eng

Identifier

(MiAaPQ)AAI3290168

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/84270