Synfacts 2008(3): 0267-0267  
DOI: 10.1055/s-2008-1042697
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Catalytic Asymmetric Allylic Alkylation with Vinylaluminum Reagents

Contributor(s):Mark Lautens, Valentina Aureggi
Y. Lee, K. Akiyama, D. G. Gillingham, M. K. Brown, A. H. Hoveyda*
Boston College, Chestnut Hill, USA
High Site- and Enantioselective Cu-Catalyzed Allylic Alkylation Reactions with Easily Accessible Vinylaluminum Reagents
J. Am. Chem. Soc.  2008,  120:  446-447  
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Publication History

Publication Date:
21 February 2008 (online)


A new efficient method for catalytic asymmetric allylic alkylation of allylic phosphates with vinylaluminum reagents is reported. The desired products are obtained in good yields and with enantioselectivities up to 98% ee.


The vinylaluminum reagents are prepared and used in situ by reaction of commercially available DIBAL-H with terminal alkynes. The asymmetric allylic alkylations are promoted in the presence of a readily available chiral N-hetero­cyclic carbene complex and a commercially available and air-stable copper salt. The desired products are obtained in relative short time (2-12 h) in 74-95% isolated yields, 77% to >98% ee, and with >98% E-selectivities. Various allylic phosphates can be used, including trisubstituted and disubstituted olefines. Vinyl bromides and cyclic alkenes are also suitable substrates for the allylic alkylation. A variety of terminal alkynes can be employed, including conjugated enynes. The hydroalumination/catalytic AAA sequence can be performed in a single vessel, on gram scale.