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

Stanisław Krompiec; Mateusz Penkala; Ewelina Kowalska; Robert Penczek; Piotr Bujak; Witold Danikiewicz; Grzegorz Spólnik; Andrzej Kita; Iwona Grudzka

doi:10.1007/s00706-011-0638-8

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

Monatsh Chem. 2011;142(12):1241-1247. doi: 10.1007/s00706-011-0638-8. Epub 2011 Oct 27.

Authors

Stanisław Krompiec¹, Mateusz Penkala¹, Ewelina Kowalska¹, Robert Penczek¹, Piotr Bujak¹, Witold Danikiewicz², Grzegorz Spólnik², Andrzej Kita¹, Iwona Grudzka¹

Affiliations

¹ Institute of Chemistry, University of Silesia, Katowice, Poland.
² Institute of Organic Chemistry, Polish Academy of Science, Warsaw, Poland.

Abstract

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.

Keywords: Chemoselectivity; Homogeneus catalysis; Metal complexes; Mixed acetals.