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. 2008 Jun 4;130(22):6940-1.
doi: 10.1021/ja802144t. Epub 2008 May 8.

Mechanistic insights into the gold-catalyzed cycloisomerization of bromoallenyl ketones: ligand-controlled regioselectivity

Yuanzhi Xia  1 , Alexander S Dudnik, Vladimir Gevorgyan, Yahong Li
Affiliations

Mechanistic insights into the gold-catalyzed cycloisomerization of bromoallenyl ketones: ligand-controlled regioselectivity

Yuanzhi Xia et al. J Am Chem Soc. .

Abstract

Through computational and experimental studies, the mechanisms of gold-catalyzed cycloisomerization of bromoallenyl ketones in toluene have been elucidated. The divergent 1,2-migrations for the Au(I)- and Au(III)-catalyzed reactions have been investigated, and the results confirmed that the regiochemistry is ligand-dependent in cases of Au(PR3)L (L = Cl, OTf, BF4, and SbF6) catalysts.

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Figures

Figure 1
Figure 1
Potential energy surfaces for AuCl3- and Au(PR’3)Cl-catalyzed cycloisomerizations (R = CH3, R’= H).
Scheme 1
Scheme 1
Regiodivergent Au(III)- and Au(I)-catalyzed cycloisomerizations of bromoallenyl ketones.
Scheme 2
Scheme 2
Experimental results of Au(I)-catalyzed reations.
See this image and copyright information in PMC

References

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