A Novel Approach to Functionalized Heterohelicenes via Chromium-Templated Benzannulation Reactions

Jochen F. Schneider; Martin Nieger; Kalle Nättinen; Karl Heinz Dötz

doi:10.1055/s-2005-861864

PAPER

A Novel Approach to Functionalized Heterohelicenes via Chromium-Templated Benzannulation Reactions [1]

Jochen F. Schneider^a, Martin Nieger^b, Kalle Nättinen^c, Karl Heinz Dötz*^a
^a Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität, 53121 Bonn, Germany
Fax: +49(228)735813; e-Mail: doetz@uni-bonn.de ;
^b Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität, 53121 Bonn, Germany
^c Department of Chemistry, University of Jyväskylä, P.O. Box 35, 40014 Jyväskylä, Finland

Abstract

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Abstract

A series of functionalized oxa- and thiaheterohelicenes has been prepared by a new progressive annulation technique based on the chromium-templated [3+2+1]benzannulation reaction of hetero[5]helicene carbene complexes with various alkynes partly in competition of angular and linear annulation. Oxidative work-up with CAN yields the respective quinones along with small amounts of nitrated products or a nitrate ester byproduct. Thermal recomplexation of an acylated monobenzannulation product by Cr(CO)₆ affords the corresponding, thermodynamically favored η⁶-oxa[6]helicene-Cr(CO)₃ complex. Bidirectional benzannulation reveals a more delicate regioselectivity and yields three different isomers including a bisquinone with an unprecedented bislinear annulation pattern. Molecular structures determined by X-ray analysis indicate a decreasing helical distortion as a result of progressive annulation, steric demand of the quinone substitution pattern (Ph>Pr>Et), or the nature of the embedded heterocycle (SO₂>S>O).

Key words

chromium carbene complexes - benzannulations - oxa-/thiaheterohelicenes - quinones - arene complexes

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