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Stereoelectronic Effects in the Iodine-Promoted Oxidation of Pentacyclic Tetrahydroisoquinolines

✍ Scribed by Oliver Koepler; Sabine Laschat; Burkhard Miehlich; Angelika Baro; Peter Fischer

Publisher
John Wiley and Sons
Year
2004
Tongue
German
Weight
198 KB
Volume
87
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

Iodine‐promoted oxidations of the pentacyclic tetrahydroisoquinolines 4a, 4b, and 10 were investigated. Whereas the all‐cis diastereoisomer 4a containing an arylamino moiety gave the iminium ion 5 as the primary product, which subsequently underwent intramolecular aminal formation to 6, the corresponding all‐trans diastereoisomer 4b epimerized to the all‐cis diastereoisomer 4a via iminium ion 7. In contrast, tetrahydroisoquinoline 10 could be cleanly oxidized to the corresponding isoquinolizidinium ion 11. Mechanistic considerations were supported by molecular‐modeling calculations.

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## Abstract A study on the mechanism of the well‐documented hypervalent iodine‐mediated allylic oxidation of glycals leading to 2,3‐dihydro‐4__H__‐pyran‐4‐ones is presented. Notable features are the isolation of ring‐contracted by‐products 6 and 7, which are produced upon oxidation of per‐__O__‐ben