高非对映选择性螯合控制的α-硅氧基酮加成反应。
Highly diastereoselective chelation-controlled additions to α-silyloxy ketones.
机构信息
P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, USA.
出版信息
J Am Chem Soc. 2011 May 25;133(20):7969-76. doi: 10.1021/ja201629d. Epub 2011 May 2.
Abstract
The polar Felkin-Anh, Cornforth-Evans, and Cram-chelation models predict that the addition of organometallic reagents to silyl-protected α-hydroxy ketones proceeds via a nonchelation pathway to give anti-diol addition products. This prediction has held true for the vast majority of additions reported in the literature, and few methods for chelation-controlled additions of organometallic reagents to silyl-protected α-hydroxy ketones have been introduced. Herein, we present a general and highly diastereoselective method for the addition of dialkylzincs and (E)-di-, (E)-tri-, and (Z)-disubstituted vinylzinc reagents to α-silyloxy ketones using alkyl zinc halide Lewis acids, RZnX, to give chelation-controlled products (dr ≥18:1). The compatibility of organozinc reagents with other functional groups makes this method potentially very useful in complex molecule synthesis.
摘要
极性费尔克纳-安恩、康恩福思-埃文斯和克拉姆螯合模型预测，有机金属试剂与硅保护的α-羟基酮的加成反应通过非螯合途径进行，得到反二醇加成产物。这一预测在文献中报道的绝大多数加成反应中都是正确的，并且很少有螯合控制的有机金属试剂与硅保护的α-羟基酮加成的方法被引入。在这里，我们提出了一种通用的和高度非对映选择性的方法，用于使用烷基锌卤化物路易斯酸 RZnX，将二烷基锌和（E）-二取代、（E）-三取代和（Z）-二取代的乙烯基锌试剂加成到α-硅氧基酮上，得到螯合控制的产物（dr≥18:1）。有机锌试剂与其他官能团的兼容性使得该方法在复杂分子合成中具有潜在的非常有用。
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