反芳香性降咕啉镍（II）配合物与卡宾的反应
Reactions of Antiaromatic Norcorrole Ni(II) Complex with Carbenes.
作者信息
Liu Si-Yu, Fukuoka Takaki, Fukui Norihito, Shin Ji-Young, Shinokubo Hiroshi
机构信息
Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan.
出版信息
Org Lett. 2020 Jun 5;22(11):4400-4403. doi: 10.1021/acs.orglett.0c01402. Epub 2020 May 11.
Norcorrole is a ring-contracted porphyrinoid, exhibiting distinct antiaromaticity. Herein, we report the reactions of -dimesitylnorcorrole Ni(II) complex with two types of carbenes: dichlorocarbene and an -heterocyclic carbene (NHC). The reaction with in-situ-generated dichlorocarbene resulted in the double insertion of two chloromethine units to provide a mixture of 5,15-dichloroporphyrin and chlorinated isopyricorroles. The nucleophilic NHC attacked the 3-position of the norcorrole core and the subsequent proton transfer furnished a nonconjugated macrocycle incorporating a diazafulvene segment.
降卟啉是一种环收缩的类卟啉，具有明显的反芳香性。在此，我们报道了二甲基降卟啉镍（II）配合物与两种卡宾的反应：二氯卡宾和N-杂环卡宾（NHC）。与原位生成的二氯卡宾反应导致两个氯亚甲基单元的双重插入，生成5,15-二氯卟啉和氯化异吡咯降卟啉的混合物。亲核性的NHC进攻降卟啉核心的3-位，随后的质子转移产生了一个包含二氮富烯片段的非共轭大环。
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