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


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.

SUBMITTER: Horino Y 

PROVIDER: S-EPMC2880645 | biostudies-literature | 2009 Mar

REPOSITORIES: biostudies-literature

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

Horino Yoshikazu Y   Yamamoto Takuya T   Ueda Kohki K   Kuroda Shigeyasu S   Toste F Dean FD  

Journal of the American Chemical Society 20090301 8


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 t  ...[more]

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