Regioselective Nucleophilic Functionalization of Antiaromatic Nickel(II) Norcorroles
Regioselective Nucleophilic Functionalization of Antiaromatic Nickel(II) Norcorroles
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DOI：
10.1002/anie.201502666
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发表时间：
2015-07-13
影响因子：
16.6
通讯作者：
Shinokubo, Hiroshi
中科院分区：
文献类型：
--
作者：
Nozawa, Ryo;Yamamoto, Keitaro;Shinokubo, Hiroshi
用氰化钾处理反芳香镍（II）去甲可咯，在没有催化剂的帮助下提供具有完美区域选择性的镍（II）3-氰基去甲可咯。镍（II）去甲可咯与苯酚或苯硫酚在碱存在下的反应也产生取代产物。去甲可咯核中的反芳族16 π共轭系统保留在官能化产物中。苯硫基的引入显著降低了HOMO-LUMO能隙，增强了近红外吸收性能。
Treatment of antiaromatic nickel(II) norcorrole with potassium cyanide provided nickel(II) 3-cyanonorcorrole with perfect regioselectivity without the help of a catalyst. The reaction of the nickel(II) norcorrole with phenol or thiophenol in the presence of a base also yielded substitution products. The antiaromatic 16 pi conjugation system in the norcorrole core was preserved in the functionalized products. Introduction of phenylthio groups significantly decreased the HOMO-LUMO gap and enhanced the near IR absorption property.