Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, Faculty of Science and Engineering, University of Groningen, Nijenborgh 4, 9747 AG Groningen , The Netherlands.
Catexel BV, BioPartner Center Leiden, Galileiweg 8, Leiden 2333 BD, The Netherlands.
Inorg Chem. 2022 May 30;61(21):8105-8111. doi: 10.1021/acs.inorgchem.2c00602. Epub 2022 May 15.
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 (HO), has received lots of attention. CPO itself is unsuitable for industrial use because of its tendency to decompose in the presence of excess HO. 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 -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.
近年来，人们希望开发环境友好的亲电氯化方法，这促使研究人员从自然界中汲取灵感。特别是，能够通过过氧化物（HO）氧化将氯离子反转为亲电基团从而进行亲电氯化的酶——氯过氧化物酶（CPO），受到了广泛关注。由于 CPO 自身在存在过量 HO 的情况下容易分解，因此不适合工业用途。随后开发了仿生配合物（CPO 活性位点模拟物），并已被证明能够成功催化亲电氯化反应，但由于合成要求过高，在经济上不可行。通过氯离子的反转和使用简单的中取代铁卟啉来产生 CPO 的假定活性氯化剂（次氯酸盐铁物种）的报道努力均未成功。相反，形成了 -氯异卟啉中间体，该中间体同样能够进行亲电氯化反应。本文讨论了朝着涉及这种新型中间体的环境友好的亲电氯化的潜在方法的最新进展。尽管这种新途径不再遵循 CPO 的机制，但它是从复制其功能的努力中发展而来的，这表明了从自然界中汲取灵感的力量。
