From allylic alcohols to aldols through a new nickel-mediated tandem reaction: synthetic and mechanistic studies

Chemistry : a European Journal
David CuperlyRené Grée

Abstract

Nickel hydride type complexes have been successfully developed as catalysts for the tandem isomerization-aldolization reaction of allylic alcohols with aldehydes. Optimization of the reaction conditions has shown that a cocatalyst, such as MgBr2, has a very positive effect on the kinetics of the reaction and in the yields of aldols. Under such optimized conditions {[NiHCl(dppe)] + MgBr(2) at 3-5 mol %)}, this reaction affords the aldols in good to excellent yields. It is a full-atom-economy-type reaction that occurs under mild conditions. Furthermore, it has a broad scope for the allylic alcohols and it is compatible with a wide range of aldehydes, including very bulky derivatives. The reaction is completely regioselective, but it exhibits a low stereoselectivity, except for allylic alcohols with a bulky substituent at the carbinol center. The use of chiral nonracemic catalysts was not successful, affording only racemic compounds. However, it was possible to use asymmetric synthesis for the preparation of optically active aldols. Various mechanistic studies have been performed using, for instance, a deuterated alcohol or a deuterated catalyst. They gave strong support to a mechanism involving first a transition-metal-mediated i...Continue Reading

References

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Citations

Jul 21, 2016·Chemical Reviews·Nathan A Eberhardt, Hairong Guan
Jul 4, 2007·Angewandte Chemie·Julien PetrignetRené Grée
Oct 24, 2008·Chemistry : a European Journal·Agnieszka BartoszewiczBelén Martín-Matute
Jan 5, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Nanna AhlstenBelén Martín-Matute
May 16, 2014·Chemistry : a European Journal·Antonio Bermejo GómezBelén Martín-Matute
Jun 25, 2016·Beilstein Journal of Organic Chemistry·M Emin CinarMichael Schmittel
Jun 23, 2011·Chemical Communications : Chem Comm·Nanna Ahlsten, Belén Martín-Matute
Apr 26, 2013·Angewandte Chemie·Nanna AhlstenBelén Martín-Matute
Mar 24, 2009·Organic Letters·Agnieszka Bartoszewicz, Belén Martín-Matute
Apr 13, 2010·Journal of the American Chemical Society·Cindy KörnerTom D Sheppard
Sep 17, 2010·Organic Letters·John H Phillips, John Montgomery
Jul 26, 2012·Organic Letters·Dongjin KangPhil Ho Lee
Mar 23, 2013·Organic Letters·Gangireddy PavanKumar ReddyRené Grée

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