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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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Published in: | Advanced synthesis & catalysis 2015-03, Vol.357 (4), p.775-781 |
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Main Authors: | , , , , , , |
Format: | Article |
Language: | English |
Subjects: | |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
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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. |
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ISSN: | 1615-4150 1615-4169 |
DOI: | 10.1002/adsc.201400849 |