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Synfacts 2014; 10(3): 0280
DOI: 10.1055/s-0033-1340772
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Asymmetric Hydrogenolysis of N-Sulfonyl Amino Alcohols Catalyzed by Palladium

Contributor(s):
Mark Lautens
,
Christine M. Le
Yu C.-B, Zhou Y.-G * Dalian Institute of Chemical Physics, P. R. of China
Palladium-Catalyzed Asymmetric Hydrogenolysis of N-Sulfonyl Aminoalcohols via Achiral Enesulfonamide Intermediates.

Angew. Chem. Int. Ed. 2013;
52: 13365-13368
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Publication History

Publication Date:
17 February 2014 (online)

 
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Key words

amino alcohols - dynamic kinetic resolution - asymmetric hydrogenolysis - palladium

Significance

Although hydrogenolysis is a common transformation in organic synthesis, few examples of asymmetric hydrogenolysis exist. This report highlights a palladium(II)-catalyzed asymmetric formal hydrogenolysis of racemic N-sulfonyl amino alcohols (±)-1, providing access to chiral amines 2 with high enantioselectivity. The formal hydrogenolysis process proceeds via acid-catalyzed dehydration, followed by palladium-catalyzed hydrogenation.


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Comment

Experimental results and deuterium-labelling studies suggest a mechanism involving both a dynamic kinetic asymmetric transformation (DYKAT) and a dynamic kinetic resolution (DKR). Acid-catalyzed dehydration of 1a provides enamide A, which can isomerize to imine B and enamide C. All of them have the potential for the hydrogenolysis furnishing the chiral amine 2a.


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