Nickel-Catalyzed Construction of Chiral 1-[6]Helicenols and Application in the Synthesis of [6]Helicene-Based Phosphinite Ligands
Nickel-Catalyzed Construction of Chiral 1-[6]Helicenols and Application in the Synthesis of [6]Helicene-Based Phosphinite Ligands
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镍催化手性1-[6]螺烯醇的构建及其在[6]螺烯基亚次膦酸酯配体合成中的应用
DOI：
10.1002/ejoc.201600677
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发表时间：
2016
影响因子：
2.8
通讯作者：
T.
中科院分区：
文献类型：
--
作者：
Tsujihara;Tetsuya; Inada-Nozaki;N.; Takehara;T.; Zhou;D.-Y.; Suzuki;T.; Kawano;T.
通过 Ni 催化的 [2+2+2] 环加成在多克规模上合成了两种 1-[6]helicenol 衍生物。 1-[6]螺旋烯醇的两种对映体都可以通过简单的光学拆分来有效制备。作为螺旋手性1-[6]螺烯醇的合成应用，开发了一类新型[6]螺烯基次膦酸酯；这些化合物代表了螺旋手性次亚膦酸酯配体的第一个例子。 Pd 催化的不对称烯丙基烷基化反应的收率高达 90%。
Two 1‐[6]helicenol derivatives were synthesized by Ni‐catalyzed [2+2+2] cycloaddition on a multigram scale. Both enantiomers of the 1‐[6]helicenols could be efficiently prepared by simple optical resolution. As a synthetic application of helically chiral 1‐[6]helicenols, a novel class of [6]helicene‐based phosphinites was developed; these compounds represent the first examples of helically chiral phosphinite ligands. Up to 90 %eewas obtained for the Pd‐catalyzed asymmetric allylic alkylation reaction.