Enantioselective Synthesis of 1,12-Disubstituted [4]Helicenes
Enantioselective Synthesis of 1,12-Disubstituted [4]Helicenes
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DOI：
10.1002/anie.201915870
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发表时间：
2020-02-20
影响因子：
16.6
通讯作者：
Alcarazo, Manuel
中科院分区：
文献类型：
--
作者：
Hartung, Thierry;Machleid, Rafael;Alcarazo, Manuel
报道了 1,12-二取代的[4]碳螺旋烯的高度对映选择性合成。该合成路线的关键步骤是Au催化的分子内炔烃加氢芳基化，通过使用TADDOL衍生的（TADDOL=α,α,α,α-四芳基-1,3-二氧戊环-4,5-二甲醇）α-阳离子亚膦酸酯作为辅助配体，实现了良好至优异的区域选择性和对映选择性。此外，适当的底物设计使得不同取代模式的[4]螺旋烯的组装成为可能，从而证明了该方法的合成效用。新制备的结构的绝对立体化学通过X射线晶体学测定，并且还报道了它们的光物理性质的表征。
A highly enantioselective synthesis of 1,12-disubstituted [4]carbohelicenes is reported. The key step for the developed synthetic route is a Au-catalyzed intramolecular alkyne hydroarylation, which is achieved with good to excellent regio- and enantioselectivity by employing TADDOL-derived (TADDOL=alpha,alpha,alpha,alpha-tetraaryl-1,3-dioxolane-4,5-dimethanol) alpha-cationic phosphonites as ancillary ligands. Moreover, an appropriate design of the substrate makes the assembly of [4]helicenes of different substitution patterns possible, thus demonstrating the synthetic utility of the method. The absolute stereochemistry of the newly prepared structures was determined by X-ray crystallography and characterization of their photophysical properties is also reported.