Diversitäts-orientierte Synthese von polycyclischen Gerüsten durch Umsetzung eines von 2,4-Dimethylphenol abgeleiteten anodischen Zwischenproduktes

Cover Picture: Diversity-Oriented Synthesis of Polycyclic Scaffolds by Modification of an Anodic Product Derived from 2,4-Dimethylphenol (Angew. Chem. Int. Ed. 6/2011)

Titelbild: Diversitäts-orientierte Synthese von polycyclischen Gerüsten durch Umsetzung eines von 2,4-Dimethylphenol abgeleiteten anodischen Zwischenproduktes (Angew. Chem. 6/2011)

ChemInform Abstract: Synthesis and Isolation of Enantiomerically Enriched Cyclopenta[b]benzofurans Based on Products from Anodic Oxidation of 2,4-Dimethylphenol.

Tetramer (I) is obtained by anodic oxidation of 2,4-dimethylphenol as reported in a previous paper.

Installation of Amine Moieties into a Polycyclic Anodic Product Derived from 2,4-Dimethylphenol

When 2,4-dimethylphenol is anodically treated, a dehydrotetramer with four contiguous stereocentres is readily obtained on a multi-gram scale. The substitution of a 2,4-dimethyl-phenoxy fragment by several amines was demonstrated, and the best results were obtained with primary amines. Optically pure α-chiral aliphatic amines yield diastereomeric mixtures that can be separated in most cases. The basic amine causes a partial hemiketal-opening of the bisbenzofuran moiety leading to an equilibrium within an α,β-unsaturated cyclohexenone. This dynamic behaviour occurs on the time scale of NMR spectroscopy and is also found by X-ray analysis providing a consistent picture.

Synthesis and Isolation of Enantiomerically Enriched Cyclopenta[b]benzofurans Based on Products from Anodic Oxidation of 2,4-Dimethylphenol

The anodic treatment of 2,4-dimethylphenol offers a powerful and direct method for the construction of a dehydrotetramer with four contiguous stereocentres on a multigram scale. The installation of propellanes on this scaffold using enantiomerically pure carbonyl compounds leads to a mixture of diastereomers. This mixture is easily separable using standard chromatography and gives rise to optically pure cyclopenta[b]benzofurans which are important scaffolds in a variety of natural products. The synthesis is easy to perform and allows a reliable access to chiral compounds with very high enantiomeric excess. It was possible to determine the absolute configuration of these compounds by compari…

Diversity-Oriented Synthesis of Polycyclic Scaffolds by Modification of an Anodic Product Derived from 2,4-Dimethylphenol

CCDC 1047644: Experimental Crystal Structure Determination

Related Article: Michael Mirion, Lars Andernach, Caroline Stobe, Joaquin Barjau, Dieter Schollmeyer, Till Opatz, Arne Lützen, Siegfried R. Waldvogel|2015|Eur.J.Org.Chem.|2015|4876|doi:10.1002/ejoc.201500600

CCDC 1047645: Experimental Crystal Structure Determination

Related Article: Michael Mirion, Lars Andernach, Caroline Stobe, Joaquin Barjau, Dieter Schollmeyer, Till Opatz, Arne Lützen, Siegfried R. Waldvogel|2015|Eur.J.Org.Chem.|2015|4876|doi:10.1002/ejoc.201500600

CCDC 1047647: Experimental Crystal Structure Determination

Related Article: Michael Mirion, Lars Andernach, Caroline Stobe, Joaquin Barjau, Dieter Schollmeyer, Till Opatz, Arne Lützen, Siegfried R. Waldvogel|2015|Eur.J.Org.Chem.|2015|4876|doi:10.1002/ejoc.201500600

CCDC 1047646: Experimental Crystal Structure Determination

Related Article: Michael Mirion, Lars Andernach, Caroline Stobe, Joaquin Barjau, Dieter Schollmeyer, Till Opatz, Arne Lützen, Siegfried R. Waldvogel|2015|Eur.J.Org.Chem.|2015|4876|doi:10.1002/ejoc.201500600