Affiliation:
1. Institut für Chemie Universität Rostock Albert-Einstein-Straße 3a 18059 Rostock Germany
2. Leibniz-Institut für Katalyse e.V. an der Universität Rostock Albert-Einstein-Straße 29a 18059 Rostock Germany
Abstract
AbstractDifferently substituted phenyl isonitriles (with C−H bonds in ortho‐position) and naphthyl isonitriles were reacted with the cyclic biradical [⋅P(μ‐N‐Ter)2P⋅] (1). Insertion of the isonitrile formed a cyclic five‐membered biradical [⋅P(NTer)2C(R)P⋅] (2R, R=phenyl, naphthyl) in the first step, followed by C−H activation at the aryl substituent, resulting in novel azaphospholes (5R), which could be isolated and fully characterized. The formation of the azaphospholes can be prevented by the addition of a second equivalent of isonitrile, which causes the blocking of the radical centers in 2R by adduct formation (3R). Quantum mechanical calculations showed that a significant increase in the aromaticity of the benzo‐ and naphtho‐azaphospholes is one of the driving forces for the activation process leading to the formation of thermodynamically favored azaphospholes. Targeted activation of C−H bonds using biradical systems represents a new synthetic approach to generate benzo‐ and naphtho‐azaphospholes.
Funder
Deutsche Forschungsgemeinschaft
Subject
General Chemistry,Catalysis,Organic Chemistry
Cited by
2 articles.
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