Platinum- and gold-catalyzed cycloisomerization reactions of hydroxylated enynes

Journal of the American Chemical Society
Victor MamaneAlois Fürstner

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.

References

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Aug 17, 2002·The Journal of Organic Chemistry·Alois Fürstner, Victor Mamane
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Citations

Dec 18, 2013·The Journal of Organic Chemistry·Li-Jing WangYong-Min Liang
Jul 26, 2008·Chemical Reviews·David J GorinF Dean Toste
Sep 8, 2005·Journal of the American Chemical Society·B A Bhanu PrasadRichmond Sarpong
Jul 28, 2005·Journal of the American Chemical Society·Anna W SromekVladimir Gevorgyan
Jan 5, 2008·Journal of the American Chemical Society·Alexander S DudnikVladimir Gevorgyan
Aug 12, 2010·Journal of the American Chemical Society·César R Solorio-Alvarado, Antonio M Echavarren
Feb 24, 2011·Journal of the American Chemical Society·Asa D MelhadoF Dean Toste
Aug 25, 2011·Journal of the American Chemical Society·Ekaterina TkatchoukF Dean Toste
Apr 12, 2012·Journal of the American Chemical Society·Roohollah Kazem ShiroodiVladimir Gevorgyan
May 9, 2012·Journal of the American Chemical Society·Dawei WangXiaodong Shi
May 1, 2013·Journal of the American Chemical Society·Weidong RaoPhilip Wai Hong Chan
Mar 11, 2008·Journal of the American Chemical Society·Paul Ha-Yeon CheongF Dean Toste
Jan 24, 2009·Journal of the American Chemical Society·Iain D G WatsonF Dean Toste
Feb 12, 2009·Journal of the American Chemical Society·Yoshikazu HorinoF Dean Toste
Feb 25, 2009·Journal of the American Chemical Society·Minoru UemuraF Dean Toste
Mar 10, 2009·Journal of the American Chemical Society·Itaru NakamuraMasahiro Terada
Oct 8, 2009·Journal of the American Chemical Society·Kazusa OtaNaoto Chatani
Jun 27, 2012·The Journal of Organic Chemistry·Elena Soriano, José Marco-Contelles
Feb 14, 2006·Organic Letters·Dong XingZhangjie Shi
Apr 21, 2006·Organic Letters·Charles FehrHorst Sommer
May 5, 2006·Organic Letters·Yuhei Miyanohana, Naoto Chatani
Dec 1, 2006·Organic Letters·Christiane M Grisé, Louis Barriault
Sep 2, 2008·Organic Letters·Steven G SethoferF Dean Toste
Jul 11, 2009·Organic Letters·Michael A TarselliMichel R Gagné
Feb 18, 2010·Nature Chemistry·Diego BenitezF Dean Toste
Feb 1, 2006·Chemical Communications : Chem Comm·Daniel KadzimirszGerald Dyker
Feb 22, 2007·Chemical Communications : Chem Comm·Matthew L MaddessMax Malacria

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