Synfacts 2008(2): 0174-0174  
DOI: 10.1055/s-2007-992486
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Cu-Catalyzed Asymmetric Allylic Substitution with Boron Nucleophiles

Contributor(s): Mark Lautens, Praew Thansandote
H. Ito*, S. Ito, Y. Sasaki, K. Matsuura, M. Sawamura*
Hokkaido University, Sapporo, Japan
Further Information

Publication History

Publication Date:
23 January 2008 (online)


The first example of a Cu(I)-catalyzed asymmetric allylic substitution with non-carbon nucleophiles is presented. Using bis(pinacolato)diboron, a Cu(I) source, and a chiral ligand, optically active α-chiral allylboronates can be synthesized in moderate yields and excellent enantio­selectivities. The paper presents a limited number of examples and the reaction appears to have high sensitivity to steric effects since it does not proceed with a bulky isopropyl group on the alkene of the allylic carbonate. However, the synthetic utility of the products is demonstrated by a Lewis acid mediated stereoselective addition to an aldehyde with high enantio- and E/Z selectivity.