Synthesis of Cyclophenacene‐ and Chiral‐Type Cyclophenylene‐Naphthylene Belts
Synthesis of Cyclophenacene‐ and Chiral‐Type Cyclophenylene‐Naphthylene Belts
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环苯并苯和手性型环亚苯基-亚萘基带的合成
DOI：
10.1002/anie.202200800
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Tanaka Ken
中科院分区：
文献类型：
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作者：
Nogami Juntaro;Nagashima Yuki;Sugiyama Haruki;Miyamoto Kazunori;Tanaka Yusuke;Uekusa Hidehiro;Muranaka Atsuya;Uchiyama Masanobu;Tanaka Ken
我们报道了[20]环苯并苯型环亚苯基-亚萘基（CPN）带的合成以及通过阳离子铑（I）催化的萘嵌入的环状多炔的分子内[2+2+2]环加成反应对映选择性地合成手性型CPN带（高达> 99%ee）。还尝试了深度扩展的CPN带的合成，但最终的分子内[2+2+2]环加成不成功。理论计算澄清，反应性取决于在初始氧化环加成步骤中的过渡态的稳定性，这是受到分子应变。这些CPN带的圆柱形结构通过X射线晶体学分析得到证实。由于在手性型CPN带中通过引入萘进行π扩展，与相应的锯齿型手性环苯带相比，电子圆二色性和圆偏振发光的各向异性不对称因子被放大。
We report the synthesis of a [20]cyclophenacene‐type cyclophenylene‐naphthylene (CPN) belt and the enantioselective synthesis of chiral‐type CPN belts (up to >99 %ee) by the cationic rhodium(I)‐catalyzed intramolecular [2+2+2] cycloaddition of naphthalene‐embedded cyclic polyynes. The synthesis of a depth‐expanded CPN belt was also attempted, but the final intramolecular [2+2+2] cycloaddition was unsuccessful. Theoretical calculations clarified that the reactivity depends on the stability of the transition state in the initial oxidative cycloaddition step which is subject to molecular strain. The cylindrical structures of these CPN belts were confirmed by X‐ray crystallographic analyses. As a result of π‐extension through the introduction of naphthalenes in the chiral‐type CPN belts, the anisotropy dissymmetry factors of electronic circular dichroism and circularly polarized luminescence are amplified compared with the corresponding zigzag‐type chiral cyclophenylene belts.