A Short Synthetic Route to (+)-Austamide, (+)-Deoxyisoaustamide, and (+)-Hydratoaustamide from a Common Precursor by a Novel Palladium-Mediated Indole → Dihydroindoloazocine Cyclization
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- 14 June 2002
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 124 (27) , 7904-7905
- https://doi.org/10.1021/ja026663t
Abstract
The first synthesis of (+)-austamide (1), (+)-deoxyisoaustamide (2), and (+)-hydratoaustamide (10) by a very direct route is described (Scheme 1). Starting from tryptophan methyl ester (3) intermediate 5 is generated in two steps in >98% overall yield. The key step in the synthesis is a novel cyclization of 5 involving organopalladium intermediates which gives the dihydroazocine 6. From this key intermediate the target structures are accessible in just a few steps as shown in Scheme 1. The remarkable conversion of 5 → 6 can be rationalized by the mechanistic pathway shown in Scheme 2 that involves a multistep sequence which includes palladation, cyclization, and rearrangement.Keywords
This publication has 6 references indexed in Scilit:
- Stereocontrolled Total Synthesis of (+)-Paraherquamide BJournal of the American Chemical Society, 1996
- Stereospecific total synthesis of dl-austamideJournal of the American Chemical Society, 1979
- Interaction between orthogonal magnetic orbitals in a copper(II)-oxovanadium(II) heterobinuclear complexJournal of the American Chemical Society, 1978
- The structures of five diketopiperazines from Aspergillus ustusTetrahedron, 1973
- The arylation of allylic alcohols with organopalladium compounds. A new synthesis of 3-aryl aldehydes and ketonesJournal of the American Chemical Society, 1968
- ORGANOMERCURIALS. VIII. MERCURY AS THE LEAVING GROUP IN SOLVOLYSIS REACTIONS1Journal of the American Chemical Society, 1961