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. 2010;49(2):419-23.
doi: 10.1002/anie.200905223.

Stereoisomerically pure trisubstituted vinylaluminum reagents and their utility in copper-catalyzed enantioselective synthesis of 1,4-dienes containing Z or E alkenes

Katsuhiro Akiyama  1 , Fang Gao, Amir H Hoveyda
Affiliations

Stereoisomerically pure trisubstituted vinylaluminum reagents and their utility in copper-catalyzed enantioselective synthesis of 1,4-dienes containing Z or E alkenes

Katsuhiro Akiyama et al. Angew Chem Int Ed Engl. 2010.
No abstract available

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Figures

Scheme 1
Scheme 1
Projected diastereo- and enantioselective synthesis of nyasol through Cu-catalyzed allylic alkylation with a cis vinylaluminum reagent. NHC=N-heterocyclic carbene, PG=protecting group.
Scheme 2
Scheme 2
Synthesis of a cis- or trans-disubstituted alkene may be accomplished through hydroalumination/desilylation of a Si-substituted alkyne.
Scheme 3
Scheme 3
Stereoselective hydroalumination of trimethylsilylphenylacetylene with dibal-H, and a rationale for the effect of a Lewis base (THF). dibal-H=(iBu)2AlH.
Scheme 4
Scheme 4
Enantioselective synthesis of (−)-nyasol, featuring a one-pot alkyne hydroalumination/Cu-catalyzed enantioselective allylic alkylation. TFA=trifluoroacetic acid.
See this image and copyright information in PMC

References

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    1. For examples of catalytic enantio-selective vinyl conjugate additions to unsaturated carbonyls, see: Oi S, Taira A, Honma Y, Inoue Y. Org. Lett. 2003;5:97–99. Oi S, Sato T, Inoue Y. Tetrahedron Lett. 2004;45:5051–5055. Otomaru Y, Hayashi T. Tetrahedron: Asymmetry. 2004;15:2647–2651. Nicolaou KC, Tang W, Dagneau P, Faraoni R. Angew. Chem. 2005;117:3942–3947. Angew. Chem. Int. Ed. 2005;44:3874–3879. Nakao Y, Chen J, Imanaka H, Hiyama T, Ichikawa Y, Duan W-L, Shintani R, Hayashi T. J. Am. Chem. Soc. 2007;129:9137–9143. Vuagnoux-d Augustin M, Alexakis A. Chem. Eur. J. 2007;13:9647–9662. Lee K.-s., Hoveyda AH. J. Org. Chem. 2009;74:4455–4462.

    1. Lee Y, Akiyama K, Gillingham DG, Brown MK, Hoveyda AH. J. Am. Chem. Soc. 2008;130:446–447. - PubMed

    1. Treatment of aryl-substituted terminal alkynes with dibal-H leads to the generation of significant amounts (≈30%) of the derived alkynylalanes. See: Zweifel G, Snow JT, Whitney CC. J. Am. Chem. Soc. 1968;90:7139–7141.

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