Reversal phenomenon of reaction velocity in a mixed reaction system: silylations between simple alcohols and alpha- or beta-hydroxyketones using anilinosilanes and catalytic TBAF agent

Akira Iida; Chihiro Hashimoto; Tomonori Misaki; Yukiteru Katsumoto; Yukihiro Ozaki; Yoo Tanabe

doi:10.1021/jo070081i

Reversal phenomenon of reaction velocity in a mixed reaction system: silylations between simple alcohols and alpha- or beta-hydroxyketones using anilinosilanes and catalytic TBAF agent

J Org Chem. 2007 Jun 22;72(13):4970-3. doi: 10.1021/jo070081i. Epub 2007 May 31.

Authors

Akira Iida¹, Chihiro Hashimoto, Tomonori Misaki, Yukiteru Katsumoto, Yukihiro Ozaki, Yoo Tanabe

Affiliation

¹ Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo 669-1337, Japan.

PMID: 17536862
DOI: 10.1021/jo070081i

Abstract

We encountered a unique phenomenon of reaction velocity reversal during the silylation between mixed simple alcohols (A; AOH) and alpha- or beta-hydroxyketones (B; BOH). The present reaction system using anilinosilanes 1a [PhNH(TMS)] (TMS-A) and 1b [PhNH(TES)] (TES-A) with the catalytic TBAF (0.02 equiv) reagent showed that the order of silylation-velocity between the independent system and the mixed system was distinctively reversed [nu(A) > nu(B) approximately nu(B(mix)) > nu(A(mix))]. A total of seven examples indicate its high generality: AOH = linalool, 3-octanol; BOH = valeroin, benzoin, 5-hydroxy-4-methyl-3-undecanone. Time-dependent IR spectroscopy analysis rationally supported this speculation.