Platinum- and gold-catalyzed cycloisomerization reactions of hydroxylated enynes.

Platinum- and gold-catalyzed cycloisomerization reactions of hydroxylated enynes. Research Abstract Details 

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Platinum- and gold-catalyzed cycloisomerization reactions of hydroxylated enynes. Abstract Text:

Victor Mamane,Tobias Gress,Helga Krause,Alois ,

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.

Platinum- and gold-catalyzed cycloisomerization reactions of hydroxylated enynes. Publishing Authors By Initials

V Mamane,T Gress,H Krause,A ,

For similar inorganic chemicals: platinum compounds research abstracts see: inorganic chemicals: platinum compounds research

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Platinum- and gold-catalyzed cycloisomerization reactions of hydroxylated enynes. Journal Published:

PUBLICATION TYPE: Research Support, Non-U.S. Gov

Journal: Journal of the American Chemical Society

VOLUME: 126

Page Numbers: 8654-5

Journal Abbreviation: J. Am. Chem. Soc.

ISSN: 0002-7863

DAY: 21

MONTH: Jul

YEAR: 2004

Platinum- and gold-catalyzed cycloisomerization reactions of hydroxylated enynes. Information

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LANGUAGE: eng

NlmUniqueID: 7503056

Platinum- and gold-catalyzed cycloisomerization reactions of hydroxylated enynes. Keywords Mesh Terms:

KEYWORDS: Platinum Compounds

MESH TERMS: chemistry

Chemical & Substance for Abstract: Platinum- and gold-catalyzed cycloisomerization reactions of hydroxylated enynes. Information

Substance Name: platinum chloride

Registry Number: 12648-47-4

Grant and Affiliation Information for Platinum- and gold-catalyzed cycloisomerization reactions of hydroxylated enynes.

AFFILIATION: Max-Planck-Institut für Kohlenforschung, D-45470 Mülheim/Ruhr, Germany.

Country: United States

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MEDLINETA: J Am Chem Soc

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