Synfacts 2015; 11(2): 0155
DOI: 10.1055/s-0034-1379778
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Copper(I)-Mediated Asymmetric Boryl Substitution of Allyl Acetals

Mark Lautens
Steffen Kress
Yamamoto E, Takenouchi Y, Ozaki T, Miya T, Ito H * Hokkaido University, Sapporo, Japan
Copper(I)-Catalyzed Enantioselective Synthesis of α-Chiral Linear or Carbocyclic (E)-(γ-Alkoxyallyl)boronates.

J. Am. Chem. Soc. 2014;
136: 16515-16521
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19. Januar 2015 (online)



The authors describe a novel Cu-mediated enantioselective and γ-selective boryl substitution of allyl acetals for the synthesis of enantioenriched α-chiral linear or carbocyclic (E)-(γ-alkoxyallyl)boronates under mild conditions. The derived chiral boronates were used in aldehyde allylation reactions rendering the respective 1,2-diol products in good yields and excellent enantioselectivity.



Z-Substituted allyl acetates gave superior results over the analogous E-substrates. This versatile strategy was highlighted by an impressive example within the modular synthesis of 3,3-disubstituted cyclopentene. In this system the strategy was used twice, formally replacing both alkoxy groups of the acetal by two subsequent boryl substitution/aldehyde allylation reactions. Exceptional enantiocontrol and high yields were obtained.