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

Arnold, Michael A.

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Description

Title

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

Author(s)

Arnold, Michael A.

Issue Date

2007

Doctoral Committee Chair(s)

Gin, David Y.

Department of Study

Chemistry

Discipline

Chemistry

Degree Granting Institution

University of Illinois at Urbana-Champaign

Degree Name

Ph.D.

Degree Level

Dissertation

Keyword(s)

Chemistry, Organic

Language

eng

Abstract

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.

Graduation Semester

2007

Type of Resource

text

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http://hdl.handle.net/2142/84270

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