Enantioselective Au-Catalyzed Synthesis of Thia[5]- and Thia[6]helicenes and Their Transformation into Bowl-shaped Pleiadenes
Enantioselective Au-Catalyzed Synthesis of Thia[5]- and Thia[6]helicenes and Their Transformation into Bowl-shaped Pleiadenes
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DOI：
10.1002/adma.202211279
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发表时间：
2023-03-17
影响因子：
29.4
通讯作者：
Alcarazo, Manuel
中科院分区：
文献类型：
--
作者：
Fu, Wei;Pelliccioli, Valentina;Alcarazo, Manuel
通过高度对映选择性的金催化分子内炔烃加氢芳基化反应，合成了一系列螺旋形苯并[b]并[4,3-d]噻吩、萘并[1,2-b]菲[4,3-d]噻吩和苯并[3,4-b]萘并[1,2-d]噻吩。所获得结构的反转势垒通过理论和实验确定，并报告了它们的手性光学性质。还介绍了这些硫杂螺旋烯的合成后官能化及其转化为氮杂螺旋烯的初步研究。此外，还开发了一种简单的一步方案，将最初获得的并[3,4-b]萘并[1,2-d]噻吩包裹成碗状昴烯衍生物，而不损害对映体纯度。以高对映选择性获得的结构相关产物的数量使得能够在结构和构象稳定性或（手性）光学性质之间建立全面的相关性。
A series of helically shaped benzo[b]chryseno[4,3-d]thiophenes, naphtho[1,2-b]phenanthro[4,3-d]thiophenes, and chryseno[3,4-b]naphtho[1,2-d]thiophenes is synthesized via a highly enantioselective Au-catalyzed intramolecular alkyne hydroarylation reaction. The inversion barriers of the structures obtained are determined both theoretically and experimentally, and their chiroptical properties are reported. Preliminary studies on the post-synthetic functionalization of these thiahelicenes and their transformation into azahelicenes are also presented. In addition, a straightforward one-step protocol is developed, which wraps the initially obtained chryseno[3,4-b]naphtho[1,2-d]thiophenes into bowl-shaped pleiadene derivatives without erosion of the enantiopurity. The number of structurally related products that are obtained with high enantioselectivity enables the establishment of comprehensive correlations between the structure and conformational stability or (chir)optical properties.