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Synfacts 2015; 11(1): 0046
DOI: 10.1055/s-0034-1379745
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Zirconium/VANOL-Catalyzed Asymmetric α-Iminol Rearrangement

Contributor(s):
Hisashi Yamamoto
,
Takayuki Furukawa
Zhang X, Staples RJ, Rheingold AL, * Wulff WD. * Michigan State University and University of California, San Diego, USA
Catalytic Asymmetric α-Iminol Rearrangement: New Chiral Platforms.

J. Am. Chem. Soc. 2014;
136: 13971-13974
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Further Information

Publication History

Publication Date:
15 December 2014 (online)

 
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Key words

α-iminol rearrangement - VANOL ligands - 1,2-carbon shift - zirconium

Significance

There has been no example of asymmetric α-iminol rearrangement so far. Herein, the authors developed an effective catalyst system, a zirconium/VANOL complex, which works well not only with α-iminols as starting material, but also with in situ generated α-iminols from an aldehyde and an aniline.


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Comment

The zirconium/VANOL catalyst affords excellent yields and enantioselectivities for a broad range of substrates. Interestingly, N-methyl imidazole coordinated to zirconium dramatically influences the reaction. When there is a para-CF3 substituent on the phenyl ring, more careful manipulations are required such as inert atmosphere and deoxygenation.


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