Sulfur ylide initiated thio-Claisen rearrangements: Synthesis of highly substituted indolines

ORGN 25

Jon D. Rainier1, Alexei V. Novikov1, and Abigail R. Kennedy2. (1) Department of Chemistry, University of Utah, 315 S 1400 E, Salt Lake City, UT 84112, (2) Exelixis, Inc, 170 Harbor Way, P.O. Box 511, So. San Francisco, CA 94083-0511

The presence of C(3) quaternary substitution in a wide variety of interesting indoline containing natural and non-natural products has inspired a number of groups, including ours, to develop new and improved routes to their synthesis. Our contributions to this area began with the somewhat surprising result that occurred when we attempted to couple vinyl diazoacetate 2 with 2-thio-3-alkylindole 1 in the presence of rhodium acetate (eq. 1). Rather than the anticipated C-S insertion product that had been observed with diazomalonates and diazo-b-ketoesters, we isolated C(3) quaternary substituted indoline 3.

(1)

This study focuses on a more in-depth look of the newly discovered reaction: its scope, mechanism and potential synthetic use.

 

Metal-Mediated Reactions and Syntheses
8:00 AM-12:00 PM, Sunday, March 23, 2003 Convention Center -- Room 352, Oral

Division of Organic Chemistry
The 225th ACS National Meeting, New Orleans, LA, March 23-27, 2003