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Synfacts 2011(7): 0737-0737
DOI: 10.1055/s-0030-1260653
DOI: 10.1055/s-0030-1260653
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag
Stuttgart ˙ New York
Copper-Catalyzed Stereospecific Allylic Alkylation of Ketene Silyl Acetals
Contributor(s):Hisashi Yamamoto, Patrick BradyD. Li, H. Ohmiya*, M. Sawamura*
Hokkaido University, Sapporo, Japan
Copper-Catalyzed γ-Selective and Stereospecific Allylic Alkylation of Ketene Silyl Acetals
J. Am. Chem. Soc. 2011, 133: 5672-5675
Hokkaido University, Sapporo, Japan
Copper-Catalyzed γ-Selective and Stereospecific Allylic Alkylation of Ketene Silyl Acetals
J. Am. Chem. Soc. 2011, 133: 5672-5675
Further Information
Publication History
Publication Date:
17 June 2011 (online)
Key words
allylic alkylation - copper - regioselectivity
Significance
Allylic alkylation of enolates is an important transformation in organic synthesis. The copper-catalyzed method described employs unsymmetrical internal allylic phosphates as electrophiles, which react with excellent γ-regioselectivity and excellent Z-diastereoselectivity.
Comment
The γ-selective allylic alkylation of chiral allylic phosphates proceeds with efficient 1,3-anti α-to-γ chirality transfer. The stereochemical outcome of the product is dependent on the E/Z geometry of the allylic phosphate. The authors propose the reaction pathway shown above, invoking an allyl copper(III) intermediate.