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Gold Catalysis: Tandem Reactions of Diyne–Diols and External Nucleophiles as an Easy Access to Tricyclic Cage-Like Structures

Authors

  • A. Stephen K. Hashmi Prof. Dr.,

    1. Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg (Germany), Fax: (+49) 6221-54-4205
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  • Miriam Bührle Dipl.-Chem.,

    1. Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg (Germany), Fax: (+49) 6221-54-4205
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  • Michael Wölfle Dr.,

    1. Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany)
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  • Matthias Rudolph Dr.,

    1. Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg (Germany), Fax: (+49) 6221-54-4205
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  • Marcel Wieteck,

    1. Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg (Germany), Fax: (+49) 6221-54-4205
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  • Frank Rominger Dr.,

    1. Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg (Germany), Fax: (+49) 6221-54-4205
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  • Wolfgang Frey Dr.

    1. Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany)
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  • The authors thank Umicore AG & Co. KG for the generous donation of gold salts.

Abstract

Different diyne–diols composed of two terminal homopropargylic alcohol groups were prepared by bi-directional synthesis. Subjection of the syn diastereomers to NAC–gold catalysts (NAC=nitrogen acyclic carbene) in the presence of external nucleophiles such as water or anilines provided substituted and highly rigid heterocyclic cages. The corresponding anti disastereomers polymerised. An intermediate of the reactions of the syn diastereomers could be isolated and even be characterised by crystal structure analysis. Overall, eight new bonds are formed in the reaction, which proceeds by a multistep sequence of highly selective hydroalkoxylations and hydrohydroxylation or hydroaminations. For furyl substituents and for internal alkynes competing reaction pathways could be identified. By the cross-coupling of a product with an iodoaryl substituent, the use of these cage compounds as geometrically defined linking groups by using orthogonal transition-metal-catalysed methodology, namely, gold and palladium catalysis, could be demonstrated.

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