From Allylic Alcohols to Aldols via a Novel, Efficient Reaction Catalyzed by Ni-Complexes

Abstract

Allylic alcohols react with aldehydes, in an atom economic aldol-type reaction, in the presence of a catalytic amount of (dppe)NiHCl/MgBr₂ mixture. This reaction occurs in good to excellent yields with total regiocontrol and very high chemo control under mild conditions. It is compatible with various types of aldehydes including very bulky ones.

Key words

allylic alcohols - double bond isomerization - aldol reaction - nickel hydrides

References

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12

The stereoisomeric ratios were established by ¹H NMR on the crude reaction mixture. The relative stereochemistries were attributed by comparison with literature data or according to the following empirical rule: The C of the CHOH group is deshielded in the anti-adduct compared to the syn-adduct and the H of the CHOH group is shielded in the anti-adduct compared to the syn-adduct.