Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Haifa, 32000, Israel.
Chemistry Department, Nuclear Research Centre Negev, P.O.B. 9001, Beer Sheva, 84190, Israel.
Angew Chem Int Ed Engl. 2018 Jan 22;57(4):1006-1010. doi: 10.1002/anie.201710106. Epub 2017 Dec 29.
Corrole and sapphyrin with the smallest meso-substituents reported so far were prepared in a one-pot synthesis that relies on a non-aldehydic precursor for introducing CF groups. The substantial amounts of products obtained by this facile pathway allowed for the full characterization of 5,10,15-tris(trifluoromethyl)corrole, the access to a variety of stable chelates thereof and investigations that disclose the unique structural and chemical properties induced by the CF substituents. The novel 5,10,15,20-tetra(trifluoromethyl)sapphyrin undergoes only single protonation, which according to its crystal structure is stabilized by favorable non-bonding F/H interaction between the meso-CF and the inverted pyrrolic NH.
迄今为止报道的具有最小中位取代基的corrole 和 sapphyrin 是通过一锅合成制备的，该合成依赖于非醛前体来引入 CF 基团。通过这种简便的方法获得了大量产物，从而可以对 5,10,15-三（三氟甲基）corrole 进行全面表征，获得了多种稳定的配合物，并进行了研究，揭示了 CF 取代基所引起的独特结构和化学性质。新型的 5,10,15,20-四（三氟甲基）sapphyrin 仅经历一次质子化，根据其晶体结构，由中位 CF 和反式吡咯 NH 之间有利的非键 F/H 相互作用稳定。
