Nogami Juntaro, Nagashima Yuki, Sugiyama Haruki, Miyamoto Kazunori, Tanaka Yusuke, Uekusa Hidehiro, Muranaka Atsuya, Uchiyama Masanobu, Tanaka Ken
Department of Chemical Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo, 152-8550, Japan.
Institute for Molecular Science, Myodaiji, Okazaki, Japan.
Angew Chem Int Ed Engl. 2022 Apr 4;61(15):e202200800. doi: 10.1002/anie.202200800. Epub 2022 Feb 28.
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.
我们报道了一种[20]环菲烯型环亚苯基 - 萘基（CPN）带的合成，以及通过阳离子铑（I）催化的嵌入萘的环状多炔的分子内[2 + 2 + 2]环加成反应对手性型CPN带的对映选择性合成（对映体过量高达>99%）。还尝试了深度扩展CPN带的合成，但最后的分子内[2 + 2 + 2]环加成反应未成功。理论计算表明，反应活性取决于初始氧化环加成步骤中过渡态的稳定性，该步骤受分子应变影响。这些CPN带的圆柱结构通过X射线晶体学分析得到证实。由于在手性型CPN带中引入萘导致π扩展，与相应的锯齿型手性环亚苯基带相比，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。
