Enantioselective Synthesis, Crystal Structures, and Stereoisomerism of Substituted o,m,o,p-Tetraphenylenes,Organic Letters

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Enantioselective Synthesis, Crystal Structures, and Stereoisomerism of Substituted o,m,o,p-Tetraphenylenes
Organic Letters ( IF 4.9 ) Pub Date : 2024-09-10 , DOI: 10.1021/acs.orglett.4c02712
Yuya Kawai ₁ , Tomohiro Oriki ₁ , Yu Sato ₁ , Juntaro Nogami ₁ , Yoshinobu Kamiya ₁ , Shunsuke Suzuki ₁ , Ken Tanaka ₁

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We have achieved the enantioselective synthesis of highly strained, substituted o,m,o,p-tetraphenylenes (≤98% ee) via the cationic Rh(I)/(R)-H₈-BINAP complex-catalyzed chemo-, regio-, and enantioselective intermolecular cross-[2+2+2] cycloaddition of teraryl diynes with dimethyl acetylenedicarboxylate. X-ray crystallographic analyses demonstrate the highly bent structures of the para-substituted benzene moieties, and density functional theory calculations reveal the large local strain of the paraphenylene unit. ¹H nuclear magnetic resonance analyses and theoretical calculations elucidate the stereoisomerism, indicating that the nonrotatable ortho-disubstituted biphenyl structure results in cis and trans isomers.

中文翻译：

取代的邻、间、邻、对四亚苯基的对映选择性合成、晶体结构和立体异构性

我们通过阳离子Rh(I)/( R )-H ₈ -BINAP复合物催化的化学-、区域-实现了高张力、取代的o 、 m 、 o 、 p-四亚苯基(≤98% ee)的对映选择性合成。，以及三芳基二炔与乙炔二甲酸二甲酯的对映选择性分子间交叉[2+2+2]环加成。 X射线晶体学分析证明了对位取代苯部分的高度弯曲结构，密度泛函理论计算揭示了对亚苯基单元的大局部应变。 ¹ H核磁共振分析和理论计算阐明了立体异构现象，表明不可旋转的邻位二取代联苯结构导致顺式和反式异构体。

更新日期：2024-09-10

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