English
 
User Manual Privacy Policy Disclaimer Contact us
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT

Released

Journal Article

Platinum- and Gold-Catalyzed Cycloisomerization Reactions of Hydroxylated Enynes

MPS-Authors
/persons/resource/persons58792

Mamane,  Victor
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons58588

Gress,  Tobias
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons58718

Krause,  Helga
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons58380

Fürstner,  Alois
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

External Ressource
No external resources are shared
Fulltext (public)
There are no public fulltexts stored in PuRe
Supplementary Material (public)

[181]SI.pdf
(Supplementary material), 117KB

Citation

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.


Cite as: http://hdl.handle.net/11858/00-001M-0000-000F-9707-E
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.