Catalytic Formation of C(sp3)–F Bonds via Heterogeneous Photocatalysis,ACS Catalysis

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Catalytic Formation of C(sp3)–F Bonds via Heterogeneous Photocatalysis
ACS Catalysis ( IF 11.3 ) Pub Date : 2018-09-20 00:00:00 , DOI: 10.1021/acscatal.8b02844
Giulia Tarantino ₁ , Ceri Hammond ₁

Affiliation

Due to their chemical, physical, and biological properties, fluorinated compounds are widely employed throughout society. Yet, despite their critical importance, current methods of introducing fluorine into compounds suffer from severe drawbacks. For example, several methods are noncatalytic and employ stoichiometric equivalents of heavy metals. Existing catalytic methods, on the other hand, exhibit poor activity, generality, selectivity and/or have not been achieved by heterogeneous catalysis, despite the many advantages such an approach would provide. Here, we demonstrate how selective C(sp³)–F bond synthesis can be achieved via heterogeneous photocatalysis. Employing TiO₂ as photocatalyst and Selectfluor as mild fluorine donor, effective decarboxylative fluorination of a variety of carboxylic acids can be achieved in very short reaction times. In addition to displaying the highest turnover frequencies of any reported fluorination catalyst to date (up to 1050 h^–1), TiO₂ also demonstrates excellent levels of durability, and the system is catalytic in the number of photons required; i.e., a photon efficiency greater than 1 is observed. These factors, coupled with the generality and mild nature of the reaction system, represent a breakthrough toward the sustainable synthesis of fluorinated compounds.

中文翻译：

非均相光催化催化形成C（sp ³）-F键

由于它们的化学，物理和生物学特性，氟化化合物在整个社会被广泛采用。然而，尽管它们具有至关重要的重要性，但是目前将氟引入化合物中的方法仍存在严重的缺点。例如，几种方法是非催化的，并且采用重金属的化学计量当量。另一方面，尽管这种方法将提供许多优点，但是现有的催化方法显示出较差的活性，通用性，选择性和/或未通过非均相催化实现。在这里，我们演示了如何通过非均相光催化实现选择性的C（sp ³）–F键合成。使用TiO ₂作为光催化剂，而Selectfluor作为温和的氟供体，可以在非常短的反应时间内实现各种羧酸的有效脱羧氟化。TiO ₂除了显示迄今为止所报道的所有氟化催化剂的最高转换频率（长达1050 h ^–1）外，还表现出出色的耐久性，并且该系统在所需的光子数量上具有催化作用。也就是说，观察到光子效率大于1。这些因素，加上反应体系的一般性和温和性质，代表了对氟化化合物可持续合成的突破。

更新日期：2018-09-20

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