Syn-Dihydroxylation of Alkenes Using a Sterically Demanding Cyclic Diacyl Peroxide
Syn-Dihydroxylation of Alkenes Using a Sterically Demanding Cyclic Diacyl Peroxide
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DOI：
10.1021/acs.joc.9b01748
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发表时间：
2019-10-04
影响因子：
3.6
通讯作者：
Schreiner, Peter R.
中科院分区：
文献类型：
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作者：
Pilevar, Afsaneh;Hossein, Abolfazl;Schreiner, Peter R.
烯烃的合成二羟基化反应在有机合成中具有很高的应用价值。环酰基过氧物(CAPs)是最近出现的有希望替代通常用于这一目的的有毒金属的候选化合物。在这里，我们证明了结构要求很高的环状过氧化氢螺环[双环[2.2.1]庚烷-2，4‘-[1，2]二氧杂环戊烷]-3’，5‘-二酮(P4)可以有效地用于烯烃的双羟基化反应。试剂P4对含有β-氢的烯烃的二羟基化反应也表现出更高的选择性，而在其他CAPS中，二元醇和烯丙醇产品相互竞争。此外，对映体P4(标记为P4‘)的使用显示了P4’用于烯烃的无金属不对称双羟基化反应的潜力。
The syn-dihydroxylation of alkenes is a highly valuable reaction in organic synthesis. Cyclic acyl peroxides (CAPs) have emerged recently as promising candidates to replace the commonly employed toxic metals for this purpose. Here, we demonstrate that the structurally demanding cyclic peroxide spiro[bicyclo[2.2.1]heptane-2,4 '-[1,2]dioxolane]-3 ',5 '-dione (P4) can be effectively used for the syn-dihydroxylation of alkenes. Reagent P4 also shows an improved selectivity for dihydroxylation of alkenes bearing beta-hydrogens as compared to other CAPs, where both diol and allyl alcohol products compete with each other. Furthermore, the use of enantiopure P4 (labeled P4 ') demonstrates the potential of P4 ' for a metal-free asymmetric syn-dihydroxylation of alkenes.