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The First Halogen-Substituted Cyclotrigermenes:  A Unique Halogen Walk over the Three-Membered Ring Skeleton and Facial Stereoselectivity in the Diels−Alder Reaction

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Department of Chemistry, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan
Department of Theoretical Studies, Institute for Molecular Science, Myodaiji, Okazaki 444-8585, Japan
Cite this: J. Am. Chem. Soc. 2002, 124, 7, 1158–1159
Publication Date (Web):January 26, 2002
https://doi.org/10.1021/ja012216m
Copyright © 2002 American Chemical Society
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Abstract

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Dark red crystals of the halogen-substituted cyclotrigermenes [(tBu3Si)3Ge3X; X = Cl, Br, I] were obtained in good yields by the reaction of [(tBu3Si)3Ge3]+·TTFPB- (TTFPB- = tetrakis(2,3,5,6-tetrafluorophenyl)borate) with potassium halides (KCl, KBr, or KI) in diethyl ether. The crystal structures of the halogen-substituted cyclotrigermenes reveal a cis-bent GeGe double bond, caused by the introduction of the electronegative halogen atom on the sp3 germanium atom of cyclotrigermene. In solution, an intramolecular halogen migration over the three-membered ring skeleton was observed. Facial stereoselectivity in the Diels−Alder reaction of new cyclotrigermenes with 2,3-dimethyl-1,3-butadiene is also reported.

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The experimental procedures and spectral data of 2a−2c and 4a−4c, Tables of crystallographic data including atomic positional and thermal parameters for 2a−2c and 4a−4c (PDF). X-ray crystallographic files in CIF format. This material is available free of charge via the Internet at http://pubs.acs.org.

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