Palladium-Catalyzed Reduction of Allylic Esters

The palladium catalyzed reduction of allylic esters provides a convenient method to access chiral olefins.¹Hayashi et al. studied the activity of the MOP ligand with palladium toward the reduction of allylic esters.² Mechanistic studies of the reaction have showed that a monodentate phosphine ligand is essential to achieve high selectivity. Reacting geranyl methyl carbonate with Pd₂(dba)₃ and MOP (1 mol% respectively), quantitatively yielded (S)-3,7-dimethyl-1,6-octadiene with 76%ee (Scheme 2). It is important to note that a low catalyst and ligand loading with mild conditions is necessary for good selectivity.

Scheme 2.

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Materials

Aldrich ChemFiles 2008, 8.6, 4.

References

1. Tsuji, J. Palladium Reagents and Catalysts; Wiley: New York, 1995.
2. Hayashi, T. et al. J. Am. Chem. Soc. 1994, 116, 775. Hayashi, T. et al. Synthesis 1994, 526.

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