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A New Concept for the Efficient Synthesis of Chiral Phosphorus−Nitrogen−Carbon Cage Compounds
Author(s) -
Hoffmann Nils,
Wismach Catleen,
Ernst Ludger,
Schiebel HansMartin,
Jones Peter G.,
Streubel Rainer
Publication year - 2003
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200200649
Subject(s) - chemistry , intramolecular force , nitrogen , yield (engineering) , intermolecular force , thermal decomposition , phosphorus , crystal structure , carbon fibers , decomposition , cage , elemental analysis , medicinal chemistry , stereochemistry , organic chemistry , molecule , composite number , metallurgy , composite material , materials science , mathematics , combinatorics
A new concept for the efficient synthesis of a chiral phosphorus‐nitrogen‐carbon cage‐compound is reported, which is comprised of a high‐yield three‐step procedure starting from a P ‐Cp*‐substituted 2 H ‐azaphosphirene complex. Thermolysis of a solution of the latter complex in the presence of Ph 3 PNCN and DMAD afforded the P ‐Cp*‐substituted 2 H ‐1,2‐azaphosphole complex 11 in a clean reaction; a further reaction at 75 °C with DMAD produced complex 12 via an intermolecular Diels−Alder reaction of the Cp* group. A subsequent intramolecular Diels−Alder reaction of 12 , at 120 °C, yielded the title compound, complex 13, in quantitative yields. Elemental analyses and detailed (solution) NMR spectroscopic and MS investigations confirmed all complexes. Furthermore, solid state structures of complexes 11 and 13 were established by X‐ray single crystal structure analyses. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)