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. 2009 Mar 4;131(8):2809-11.
doi: 10.1021/ja808780r.

Au(I)-Catalyzed cycloisomerizations terminated by sp(3) C-H bond insertion

Yoshikazu Horino  1 , Takuya Yamamoto, Kohki Ueda, Shigeyasu Kuroda, F Dean Toste
Affiliations

Au(I)-Catalyzed cycloisomerizations terminated by sp(3) C-H bond insertion

Yoshikazu Horino et al. J Am Chem Soc. .

Abstract

The gold(I)-catalyzed cycloisomerization of 1,5-enynes and 1,4-allylallenes to tetracyclododecane and tetracyclotridecane derivatives, respectively, is reported. Complexation of the cationic gold(I) complex to either the alkyne or allene moiety induces an intramolecular addition of the alkene, leading to a gold(I)-stabilized carbenoid intermediate. This intermediate undergoes a formal sp(3) C-H insertion to generate the tetracyclic adduct. A series of deuterium labeling experiments showed that the C-H functionalization step proceeds with an inverse kinetic isotope effect.

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Figures

Figure 1
Figure 1
ORTEP of 2l. Hydrogens are omitted for clarity (CCDC-703-508).
Scheme 1
Scheme 1
Mechanistic Proposal for Au(I)-Catalyzed Cycloisomerization.
See this image and copyright information in PMC

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