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  Platinum- and Gold-Catalyzed Cycloisomerization Reactions of Hydroxylated Enynes

Mamane, V., Gress, T., Krause, H., & Fürstner, A. (2004). Platinum- and Gold-Catalyzed Cycloisomerization Reactions of Hydroxylated Enynes. Journal of the American Chemical Society, 126(28), 8654-8655. doi:10.1021/ja048094q.

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 Creators:
Mamane, Victor1, Author              
Gress, Tobias1, Author              
Krause, Helga1, Author              
Fürstner, Alois1, Author              
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1Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445584              

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 Abstract: Exposure of enynes containing a hydroxyl group at one of the propargylic positions to catalytic amounts of either PtCl2 or (PPh3)AuCl/AgSbF6 results in a selective rearrangement with formation of bicyclo[3.1.0]hexan-3-one derivatives. The same products are obtained by a “one-pot” process on treatment of an alkynal with allylchlorodimethylsilane (4) and PtCl2 via a reaction cascade involving an initial platinum-catalyzed allylation followed by the cycloisomerization of the homoallylic alcohol formed in situ. This novel skeletal reorganization process was implemented into a concise total synthesis of the terpenes sabinone (18) and sabinol (19). Furthermore it is shown that conversion of the hydroxylated enynes into the corresponding acetates followed by reaction with a cationic gold catalyst formed from (PPh3)AuCl and AgSbF6 opens entry into isomeric products bearing the ketone function at the C-2 position of the bicyclo[3.1.0]hexane skeleton. The outcome of a deuterium labeling experiment and the analysis of the stereochemical course of the cycloisomerization reaction are consistent with the formation of cyclopropylmethyl platinum carbene species as reactive intermediates.

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Language(s): eng - English
 Dates: 2004-04-022004-06-252004-07-21
 Publication Status: Published in print
 Pages: 2
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: eDoc: 218441
DOI: 10.1021/ja048094q
ISI: 000222704700032
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Title: Journal of the American Chemical Society
  Other : J. Am. Chem. Soc.
  Abbreviation : JACS
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 126 (28) Sequence Number: - Start / End Page: 8654 - 8655 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870