Selective Substitution of Corroles: Nitration, Hydroformylation, and Chlorosulfonation

This work demonstrates the feasibility and powerfulness of electrophilic substitution on the
peripheral carbon atoms of triarylcorroles as a synthetic tool to new derivatives. The large difference in the
reactivity of the various carbon atoms on the macrocycle was shown to be of electronic rather than steric
origin. A careful choice of reagents and a delicate control of reaction conditions allowed the selective
syntheses of novel derivatives, in all of which substitution took place selectively in only the directly joined
pyrrole rings of the macrocycle. This was proven by a combination of X-ray crystallography of the various
products and detailed analysis of their NMR spectra.

本研究证实了在三芳基咔咯（triarylcorroles）的外围碳原子上开展亲电取代反应，以此作为制备新型衍生物合成手段的可行性与强大效能。研究表明，该大环上不同碳原子的反应活性差异源自电子效应而非空间位阻。通过审慎选择试剂并精准调控反应条件，可选择性合成各类新型衍生物，所有产物的取代反应均仅发生在大环直接相连的吡咯环上。这一结论通过对各产物的X射线晶体学（X-ray crystallography）分析，以及对其核磁共振波谱（NMR spectra）的详细解析得到了验证。