1. Academic Validation
  2. Toward Environmentally Benign Electrophilic Chlorinations: From Chloroperoxidase to Bioinspired Isoporphyrins

Toward Environmentally Benign Electrophilic Chlorinations: From Chloroperoxidase to Bioinspired Isoporphyrins

  • Inorg Chem. 2022 May 30;61(21):8105-8111. doi: 10.1021/acs.inorgchem.2c00602.
Silène Engbers 1 Ronald Hage 1 2 Johannes E M N Klein 1
Affiliations

Affiliations

  • 1 Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, Faculty of Science and Engineering, University of Groningen, Nijenborgh 4, 9747 AG Groningen , The Netherlands.
  • 2 Catexel BV, BioPartner Center Leiden, Galileiweg 8, Leiden 2333 BD, The Netherlands.
Abstract

Recent desires to develop environmentally benign procedures for electrophilic chlorinations have encouraged researchers to take inspiration from nature. In particular, the Enzyme chloroperoxidase (CPO), which is capable of electrophilic chlorinations through the umpolung of chloride by oxidation with hydrogen peroxide (H2O2), has received lots of attention. CPO itself is unsuitable for industrial use because of its tendency to decompose in the presence of excess H2O2. Biomimetic complexes (CPO active-site mimics) were then developed and have been shown to successfully catalyze electrophilic chlorinations but are too synthetically demanding to be economically viable. Reported efforts at generating the putative active chlorinating agent of CPO (an iron hypochlorite species) via the umpolung of chloride and using simple meso-substituted iron porphyrins were unsuccessful. Instead, a meso-chloroisoporphyrin intermediate was formed, which was shown to be equally capable of performing electrophilic chlorinations. The current developments toward a potential method involving this novel intermediate for environmentally benign electrophilic chlorinations are discussed. Although this novel pathway no longer follows the mechanism of CPO, it was developed from efforts to replicate its function, showing the power that drawing inspiration from nature can have.

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