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Reductive cleavage versus hydrogenation of allyl aryl ethers and allylic esters using sodium borohydride/catalytic ruthenium(III) in various aqueous solvent mixtures

✍ Scribed by James H. Babler; Nicholas A. White; Eric Kowalski; Jeffrey R. Jast


Publisher
Elsevier Science
Year
2011
Tongue
French
Weight
357 KB
Volume
52
Category
Article
ISSN
0040-4039

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✦ Synopsis


The reduction of allyl aryl ethers using sodium borohydride in the presence of a catalytic amount of ruthenium(III) chloride in various aqueous solvent mixtures at 0 °C was examined. In aqueous tetrahydrofuran, hydrogenation was the favored pathway (85-100% yield of the corresponding aryl propyl ether); whereas in aqueous N-methylformamide, reductive cleavage predominated (4:1 mixture of phenolic product/aryl propyl ether). In order to gain some insight into the mechanism for this process, 3-octyn-1-ol and trans-2-decen-1-yl acetate were subjected to similar reductive conditions; and both substrates afforded products inconsistent with a single-electron-transfer mechanism.