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Gold Catalysis: Tandem Reactions of Diyne–Diols and External Nucleophiles as an Easy Access to Tricyclic Cage‐Like Structures
Author(s) -
Hashmi A. Stephen K.,
Bührle Miriam,
Wölfle Michael,
Rudolph Matthias,
Wieteck Marcel,
Rominger Frank,
Frey Wolfgang
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201001322
Subject(s) - diastereomer , nucleophile , chemistry , catalysis , substituent , carbene , coupling reaction , combinatorial chemistry , stereochemistry , medicinal chemistry , polymer chemistry , organic chemistry
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.