Temporary Sulfur Connection in an Intramolecular SN2-Reaction. A Stereocontrolled Synthesis of (±)-Kainic Acid

Mario D. Bachi; Artem Melman

doi:10.1055/s-1996-5314

Synlett 1996; 1996(1): 60-62
DOI: 10.1055/s-1996-5314

letter

© Georg Thieme Verlag, Rüdigerstr. 14, 70469 Stuttgart, Germany. All rights reserved. This journal, including all individual contributions and illustrations published therein, is legally protected by copyright for the duration of the copyright period. Any use, exploitation or commercialization outside the narrow limits set by copyright legislation, without the publisher's consent, is illegal and liable to criminal prosecution. This applies in particular to photostat reproduction, copying, cyclostyling, mimeographing or duplication of any kind, translating, preparation of microfilms, and electronic data processing and storage.

Temporary Sulfur Connection in an Intramolecular S_N2-Reaction. A Stereocontrolled Synthesis of (±)-Kainic Acid

Mario D. Bachi^* , Artem Melman

^*Department of Organic Chemistry, The Weizmann Institute of Science, Rehovot 76100, Israel

Abstract

PDF Download All articles of this category

Homolytic isomerization of isocyanide 7 affords 2β-t-butoxycarbonyl-3β-(t9-butyldimethylsilyloxy)-4α-isopropenyl-5-ethylthio-4H-2,3-dihydropyrrole (8). The conversion of key intermediate 8 into (±)-kainic acid (3) involves, inter alia, temporary sulfur connection of an acetic acid moiety to the chiral isopropylene anchor, followed by its regio- and stereospecific intramolecular bonding to the pyrrolidine backbone. The acetic acid moiety is eventually disconnected from its anchor with concomitant regeneration of the isopropylene group by a new samarium(II) iodide-mediated tandem reductive elimination.

samarium(II) iodide - radical cyclization - tandem elimination - thiyl radical - alkenyl isocyanide

PDF (221 kb)