三氟甲磺酸铟（Bi(OTf)3）、三氟甲磺酸（TfOH）和三甲基硅基三氟甲磺酸酯（TMSOTf）介导的一锅法环氧化物重排、加成和分子内硅基化 Sakurai（ISMS）级联反应制备二氢吡喃：催化剂的比较和 Bi(OTf)3 的作用。
Bi(OTf)3-, TfOH-, and TMSOTf-mediated, one-pot epoxide rearrangement, addition, and intramolecular silyl-modified Sakurai (ISMS) cascade toward dihydropyrans: comparison of catalysts and role of Bi(OTf)3.
机构信息
Department of Chemistry, The College of William & Mary, Williamsburg, Virginia 23187-8795, USA.
出版信息
J Org Chem. 2011 Nov 18;76(22):9269-77. doi: 10.1021/jo201478d. Epub 2011 Oct 25.
Abstract
Catalytic quantities of bismuth(III) triflate efficiently initiate the rearrangement of epoxides to aldehydes, which subsequently react with (Z)-δ-hydroxyalkenylsilanes to afford 2,6-disubstituted 3,6-dihydro-2H-pyrans. Isolated yields of desired products using Bi(OTf)(3) were compared with yields obtained when the reactions were run with TfOH and TMSOTf in the presence and absence of several additives. These studies, as well as NMR spectroscopic analyses, indicate an initial Lewis acid/base interaction between Bi(OTf)(3) and substrates providing TfOH in situ.
摘要
三氟甲磺酸铋（III）作为催化量能有效地引发环氧化物重排为醛，随后醛与（Z）-δ-羟基烯基硅烷反应生成 2,6-二取代 3,6-二氢-2H-吡喃。使用 Bi(OTf)(3) 时，所需产物的分离产率与在 TfOH 和 TMSOTf 存在和不存在几种添加剂的情况下进行反应时获得的产率进行了比较。这些研究以及 NMR 光谱分析表明，Bi(OTf)(3)与底物之间存在初始路易斯酸碱相互作用，从而原位提供 TfOH。
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