Department of Chemistry, University of Kansas , 1251 Wescoe Hall Drive, Lawrence, Kansas 66054-7582, United States.
Org Lett. 2017 May 19;19(10):2556-2559. doi: 10.1021/acs.orglett.7b00852. Epub 2017 May 4.
The development of a P-tether-mediated, iterative S2'-cuprate alkylation protocol for the formation of 1,3-skipped polyol stereotetrads is reported. This two-directional synthetic strategy builds molecular complexity from simple, readily prepared C-symmetric dienediols and unites the chemistry of both temporary phosphite-borane tethers and temporary phosphate tethers-through an oxidative "function switch" of the P-tether itself-to generate intermediates that were previously inaccessible via either method alone.
本文报道了一种 P-键介导的、迭代的 S2'-杯芳烃烷基化反应,用于构建 1,3-桥连多醇立体四元环。这种双向合成策略从简单易得的 C 对称二烯二醇出发构建分子复杂性,并将临时膦酸酯-硼烷键和临时磷酸酯键的化学性质结合起来——通过 P-键自身的氧化“功能切换”——生成了以前通过任何一种方法都无法获得的中间体。