Mapp Alex, Wilmore Jamie T, Beer Paul D, Goicoechea Jose M
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Rd., Oxford, OX1 3TA, UK.
Department of Chemistry, Indiana University, 800 East Kirkwood Ave., Bloomington, IN, 47405, USA.
Angew Chem Int Ed Engl. 2023 Sep 18;62(38):e202309211. doi: 10.1002/anie.202309211. Epub 2023 Aug 11.
We describe the use of the cyaphide-azide 1,3-dipolar cycloaddition reaction for the synthesis of a new class of inorganic rotaxanes containing gold(I) triazaphosphole stoppers. Electron-deficient bis-azides, which thread perethylated pillar[5]arene in aromatic solvents, readily react with two equivalents of Au(IDipp)(CP) (IDipp=1,3-bis-(2,6-diisopropylphenyl)-imidazol-2-ylidene) to afford interlocked molecules via an inorganic click reaction. These transformations proceed in good yields (ca. 65 %) and in the absence of a catalyst. The resulting organometallic rotaxanes are air- and moisture-stable and can be purified by column chromatography under aerobic conditions. The targeted rotaxanes were characterized by multi-element nuclear magnetic resonance (NMR) spectroscopy, mass-spectrometry, and single-crystal X-ray diffraction.
我们描述了利用氰化物-叠氮化物1,3-偶极环加成反应来合成一类新型的含有金（I）三氮杂磷环终止剂的无机轮烷。缺电子的双叠氮化物在芳香溶剂中穿入全乙基化的柱[5]芳烃，它很容易与两当量的Au(IDipp)(CP)（IDipp = 1,3-双-(2,6-二异丙基苯基)-咪唑-2-亚基）反应，通过无机点击反应得到互锁分子。这些转化反应产率良好（约65%）且无需催化剂。所得的有机金属轮烷对空气和湿气稳定，并且可以在有氧条件下通过柱色谱法纯化。通过多元素核磁共振（NMR）光谱、质谱和单晶X射线衍射对目标轮烷进行了表征。
