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Synlett 2012(7): 990-1006  
DOI: 10.1055/s-0031-1290657
ACCOUNT
© Georg Thieme Verlag Stuttgart ˙ New York

Copper-Catalyzed Cycloisomerizations of Enynols and Their Esters

Charles Fehr*
Firmenich SA, Corporate R&D Division, P. O. Box 239, 1211 Geneva 8, Switzerland
Fax: +41(22)7803334; e-Mail: charles.fehr@firmenich.com; e-Mail: cgfehr@bluewin.ch;
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Publikationsverlauf

Received 11 September 2011
Publikationsdatum:
05. April 2012 (online)

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Abstract

We have discovered that several platinum- or gold-catalyzed cycloisomerization reactions can also be catalyzed by copper. This Account discusses our new findings, the complementarity of copper-catalysis, and its application to the synthesis of (-)-cubebol, (-)-β-santalol, and other fragrance compounds.

1 Introduction

2 Cycloisomerization of 5-en-1-yn-3-ols: The Cyclopropanation Pathway

3 Cycloisomerization of 5-En-1-yn-3-ol-Derived Esters and Synthesis of (-)-Cubebol

4 Cycloisomerization of a 6-En-1-yn-3-ol and Its Corresponding Acetate towards the Synthesis of Thujopsanone-Like Compounds

5 Cyclization-Fragmentations of 5-En-1-yn-3-ols

6 Synthesis of (-)-β-Santalol by Cyclization-Fragmentation of a 5-En-1-yn-3-ol

7 Reactivity of 6-En-1-yn-4-ols: Cyclization-Fragmentation vs. Metathesis Reaction

8 Conclusions and Outlook

Key words

copper catalysis - cycloisomerizations - fragrances - alkynes - gold catalysis

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Surprisingly, 90 and to a larger extent 91 showed a diminished ee as compared to 88 and 89, although the dr remained the same. Possibly, 90 and 91 undergo a thermal 1,2-H shift.

26

Migration of the cyclopropane C-C bond opposite to the C-C=M bond in 99b (Scheme  [²7] ) and 105b (Scheme  [²8] ) leads to the same metathesis product. These reactions proceed via nonclassical cations, but for clarity we prefer not to draw partial bonds.

28

Kindly performed by Professor M. Santelli (University of Aix-Marseille, France).