Intermolecular oxidative dehydrogenative 3,3 '-coupling of benzo[b]furans and benzo[b]thiophenes promoted by DDQ/H+ : total synthesis of shandougenine B

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Wirtanen , T , Muuronen , M , Hurmalainen , J , Tuononen , H M , Nieger , M & Helaja , J 2016 , ' Intermolecular oxidative dehydrogenative 3,3 '-coupling of benzo[b]furans and benzo[b]thiophenes promoted by DDQ/H+ : total synthesis of shandougenine B ' , Organic Chemistry Frontiers , vol. 3 , no. 12 , pp. 1738-1745 . https://doi.org/10.1039/c6qo00331a

Title: Intermolecular oxidative dehydrogenative 3,3 '-coupling of benzo[b]furans and benzo[b]thiophenes promoted by DDQ/H+ : total synthesis of shandougenine B
Author: Wirtanen, T.; Muuronen, M.; Hurmalainen, J.; Tuononen, H. M.; Nieger, M.; Helaja, J.
Contributor: University of Helsinki, Department of Chemistry
University of Helsinki, Department of Chemistry
University of Helsinki, Department of Chemistry
University of Helsinki, Department of Chemistry
Date: 2016
Language: eng
Number of pages: 8
Belongs to series: Organic Chemistry Frontiers
ISSN: 2052-4110
URI: http://hdl.handle.net/10138/224393
Abstract: With an excess of a strong acid, 2,3-dichloro-5,6-dicyano-1,4-quinone (DDQ) is shown to promote metal-free intermolecular oxidative dehydrogenative (ODH) 3,3'-coupling of 2-aryl-benzo[b]furans and 2-aryl-benzo[b]thiophenes up to 92% yield as demonstrated with 9 substrates. Based on the analysis of oxidation potentials and molecular orbitals combined with EPR, NMR and UV-Vis observations, the studied reaction is initiated by a DDQ-substrate charge transfer complex and presumably proceeds via oxidation of the substrate into an electrophilic radical cation that further reacts with another molecule of a neutral substrate. The coupling reactivity can easily be predicted from the oxidation potential of the substrate and the morphology of its frontier molecular orbitals. The intermolecular ODH coupling reaction allowed a concise total synthesis of the natural product shandougenine B.
Subject: CATALYZED STEREOSELECTIVE REACTIONS
C BOND FORMATION
ELECTRON-TRANSFER
DIPHOSPHINE LIGANDS
CATION-RADICALS
SCHOLL REACTION
BASIS-SETS
EFFICIENT
ACID
HETEROCYCLES
116 Chemical sciences
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