Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University , Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan.
J Org Chem. 2017 Oct 6;82(19):10425-10432. doi: 10.1021/acs.joc.7b01899. Epub 2017 Sep 21.
The regioselective halogenation of porphyrinoids is critical for their selective functionalization, which enables the fine tuning of their electronic and optical properties. Here we report the synthesis of two regioisomeric Ni(II) bromonorcorroles on the basis of the acid-induced migration of the bromo substituent. Treatment of Ni(II) dimesitylnorcorrole with N-bromosuccinimide (NBS) selectively afforded Ni(II) 3-bromonorcorrole, which was further converted into Ni(II) 2-bromonorcorrole upon treatment with hydrogen bromide. In addition, the reaction of Ni(II) dimesitylnorcorrole with an excess amount of NBS afforded the octabrominated product. The reaction mechanism of the bromination reaction of Ni(II) dimesitylnorcorrole was investigated by theoretical calculations.
卟啉类化合物的区域选择性卤化对于它们的选择性功能化至关重要，这使得可以精细调整它们的电子和光学性质。在这里，我们报告了两种区域异构体的 Ni(II) 溴代诺尔科尔的合成，这是基于溴取代基的酸诱导迁移。用 N-溴代丁二酰亚胺（NBS）处理 Ni(II) 二甲苯诺尔科尔选择性地得到 Ni(II) 3-溴代诺尔科尔，进一步用氢溴酸处理得到 Ni(II) 2-溴代诺尔科尔。此外，Ni(II) 二甲苯诺尔科尔与过量的 NBS 反应得到了八溴化产物。通过理论计算研究了 Ni(II) 二甲苯诺尔科尔的溴化反应的反应机制。
