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Gold-Catalyzed Carbenoid Transfer Reactions of Diynes - Pinacol Rearrangement versus Retro-Buchner Reaction

Aromatic diyne systems bearing one terminal propargylic acetate moiety and one tertiary propargylic alcohol subunit were converted in the presence of a gold catalyst. After an initial 1,2‐migration of the acetoxy group at the terminal alkyne, a gold carbenoid is formed which is then transferred onto...

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Bibliographic Details
Published in:Advanced synthesis & catalysis 2015-03, Vol.357 (4), p.775-781
Main Authors: Lauterbach, Tobias, Higuchi, Takafumi, Hussong, Matthias W., Rudolph, Matthias, Rominger, Frank, Mashima, Kazushi, Hashmi, A. Stephen K.
Format: Article
Language:English
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Summary:Aromatic diyne systems bearing one terminal propargylic acetate moiety and one tertiary propargylic alcohol subunit were converted in the presence of a gold catalyst. After an initial 1,2‐migration of the acetoxy group at the terminal alkyne, a gold carbenoid is formed which is then transferred onto the internal alkyne of the propargylic alcohol. This combination enables the use of propargylic acetates as precursors for a gold‐catalyzed pinacol‐type rearrangement. In the final pinacol‐like step the shift of an alkyl or aryl moiety onto an electrophilic gold carbenoid/cation terminates the reaction and 1‐naphthyl ketones are obtained as products. If electron‐rich aromatic backbones are used, a mechanistically interesting alternative pathway including a retro‐Buchner reaction is opened.
ISSN:1615-4150
1615-4169
DOI:10.1002/adsc.201400849