Unravelling reaction selectivities via bio-inspired porphyrinoid tetradentate frameworks
Unravelling reaction selectivities via bio-inspired porphyrinoid tetradentate frameworks
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DOI：
10.1016/j.ccr.2021.214239
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发表时间：
2022-01
影响因子：
20.6
通讯作者：
P. Verma;Sanghapal D. Sawant
中科院分区：
文献类型：
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作者：
P. Verma;Sanghapal D. Sawant
对于理想化学反应的进化来说，选择性是最具挑战性的任务之一，尤其是试剂在两种不同反应物或官能团存在的情况下所表现出的辨别能力是非常麻烦的。高度智能的自然系统克服了生物催化剂的选择性问题，主要是用细胞色素等卟啉催化氧化还原过程、二氧化碳的运输、过氧化氢的破坏、电子转移反应等，所有形式的生命都依赖于它。这些生物催化剂巧妙地为特定的底物量身定做，具有很高的立体选择性、区域选择性和化学选择性。卟啉是一种四齿、非常稳定的π偶联大环化合物，可以容纳中心腔中几乎所有的金属，并在结构上提供了高度的结构灵活性，这有助于在非常广泛的范围内获得化学和生物参数。当涉及到化学转化的选择性时，自然系统的运行方式与实验室系统完全不同。使用合成的卟啉类化合物模拟与天然卟啉络合物相关的生物启发化学，为其他催化选择提供了经济有效、可靠的替代方案。这些卟啉类化合物现在被很好地记录下来，并为各种重要的有机转化创造了催化剂的空间，如选择性地直接激活失活的Cone键H键(羟化、卤化、氰化等)、氧化、还原、Cone键C和Cone键N偶联、化学物质的精制等。虽然，一些研究人员汇编了卟啉类化合物的不同方面，但它们在决定反应选择性方面的贡献是一个有趣的描述。在这里，我们的目标是解析在化学反应中导致选择性产生的卟啉类化合物的结构成分，并描述这些卟啉类化合物是如何通过机械考虑来控制选择性的。
Selectivity is one of the most challenging tasks to attain for the evolution of an ideal chemical reaction and particularly the discrimination exhibited by a reagent in the presence of two different reactants or functional groups is extremely troublesome. Highly intelligent natural systems overcomes selectivity issues with biological catalysts, predominantly with porphyrins such as cytochromes, catalyzing the oxidation–reduction processes, transport of dioxygen, destruction of peroxide, electron transfer reactions etc. and all form of life depends on it. These biological catalysts smartly tailored on the way to specific substrate and exert high levels of stereo-, regio- and chemo-selectivity. Porphyrins are tetradentate, very stable π-conjugated macrocyclic compounds that can accommodate almost all metals in their central cavity and offer a high architectural flexibility in structure, which facilitates the chemical and biological parameters over a very broad range. Natural systems functions rather in a different way over the laboratory systems when it comes to entail selectivity in chemical conversions. Mimicking the bio-inspired chemistry associated with natural porphyrin complexes using synthetic porphyrinoids provide the cost effective, reliable alternatives to the other catalytic options. These porphyrinoid complexes are now well documented and creating their space as catalyst for various important organic transformations such as selective direct activation of inactivated Csingle bondH bonds (hydroxylation, halogenations, cyanation etc), oxidations, reductions, Csingle bondC and Csingle bondN couplings, refining of chemicals etc. Although, some researchers have compiled the different aspects of porphyrinoids, however, their contribution in deciding the reaction selectivities is an interesting idea to describe. Herein, our aim is to resolve the structural components of porphyrinoids accountable for the generation of selectivities in a chemical reaction and to describe how these porphyrinoids are controlling the selectivities through mechanistic considerations.