Synthesis of unsymmetrical alkyl acetals via addition of primary alcohols to allyl ethers mediated by ruthenium complexes

Abstract

Ru-catalyzed synthesis of mixed alkyl–alkyl acetals via addition of primary alcohols to allyl ethers has been extended to include long-chain and/or functionalized substrates. The catalytic systems for these reactions were generated from RuCl2(PPh3)3 and [RuCl2(1,5-COD)]x and phosphines [PPh3 or P(p-chlorophenyl)3] or SbPh3 . Of particular importance is the almost quantitative elimination of transacetalization. The addition proceeds through allyl complexes, not via isomerization of allyl ethers––subsequent addition of ROH to vinyl ethers.