Synfacts 2015; 11(1): 0048
DOI: 10.1055/s-0034-1379750
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Asymmetric Conjugate Addition of Dimethylzinc to (Z)-Nitroalkenes

Contributor(s):
Hisashi Yamamoto
,
Yasushi Shimoda
Zeng X, * Gao JJ, Song JJ, Ma S, Desrosiers J.-N, Mulder JA, Rodriguez S, Herbage MA, Haddad N, Qu B, Fandrick KR, Grinberg N, Lee H, Wei X, Yee NK, Senanayake CH. Boehringer Ingelheim Pharmaceuticals, Ridgefield, USA
Remarkable Enhancement of Enantioselectivity in the Asymmetric Conjugate Addition of Dimethylzinc to (Z)-Nitroalkenes with a Catalytic [(MeCN)4Cu]PF6–Hoveyda Ligand Complex.

Angew. Chem. Int. Ed. 2014;
53: 12153-12157
Further Information

Publication History

Publication Date:
15 December 2014 (online)

 

Significance

Asymmetric conjugate addition of organometallic species to nitroalkenes can be an efficient way to access all-carbon quaternary stereocenters. Herein, the authors demonstrate that the use of [(MeCN)4Cu]PF6 plays a crucial role in the asymmetric conjugate addition of dimethylzinc to (Z)-nitroalkenes with the Hoveyda ligand.


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Comment

With the reported conditions, the undesired nitroalkene isomerization, resulting in low enantioselectivity, has been solved. The authors also developed a practical and highly controlled method for the synthesis of (Z)-nitroalkenes (Z/E ratio ≥ 99:1).


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