Synfacts 2009(9): 0987-0987  
DOI: 10.1055/s-0029-1217639
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart ˙ New York

Ir-Catalyzed Cross-Coupling of Styrene Derivatives with Allylic Carbonates

Contributor(s):Mark Lautens, Jacki Kitching
H. He, W.-B. Liu, L.-X. Dai, S.-L. You*
Shanghai Institute of Organic Chemistry, P. R. of China
Ir-Catalyzed Cross-Coupling of Styrene Derivatives with Allylic Carbonates: Free Amine Assisted Vinyl C-H Bond Activation
J. Am. Chem. Soc.  2009,  131, 8346-8347  
Further Information

Publication History

Publication Date:
21 August 2009 (online)


Significance

The iridium-catalyzed cross-coupling of o-amino-styrene derivatives with allylic carbonates is described. The procedure affords skipped Z,E-dienes with the exclusive formation of a cis double bond.

Comment

This protocol has a broad substrate scope and affords the desired products in good yield. It is noteworthy that less of the isomerized byproducts were observed in reactions involving aliphatic allylic carbonates. The proposed mechanism involves an iridium-catalyzed amine-assisted vinyl C-H bond activation process, a notion that is supported by deuterium labeling experiments.