Supramolecular Photochemistry as a Potential Synthetic Tool: Photocycloaddition
Supramolecular Photochemistry as a Potential Synthetic Tool: Photocycloaddition
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DOI：
10.1002/chin.201647265
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发表时间：
2016-11
期刊：
影响因子：
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通讯作者：
V. Ramamurthy;J. Sivaguru
中科院分区：
文献类型：
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作者：
V. Ramamurthy;J. Sivaguru
光化学在光合作用、视觉、照相平版印刷术、光动力疗法等自然和人为事件中具有重要的应用，在实验室合成小分子的过程中，它还没有成为一种常用的工具。在其他理由中，不能用温度、溶剂、添加剂等影响光化学反应，劝阻化学家使用光引发反应作为常规合成工具。这篇综述强调了如何多样的，高度有组织的结构，如无溶剂晶体和水溶性主客体组件可以用来控制和操纵光反应，从而作为一个有效的工具，化学家，包括那些感兴趣的合成。介质在改变有机分子的激发态行为中的功效用一般的光环加成和特别是[2 + 2]光环加成来说明，反应广泛用于合成复杂的天然产物以及高度受限的分子，作为示例。在绿色可持续化学的背景下高度相关的反应介质包括无溶剂的晶体和固体，例如二氧化硅、粘土和沸石，以及可以在水中溶解和预组织疏水反应物的水溶性主体。由于没有其他试剂比光更可持续，也没有其他介质比水更绿色，我们相信这里阐述的超分子光化学在未来作为合成工具具有重要作用。
Photochemistry, bearing significant applications in natural and man-made events such as photosynthesis, vision, photolithography, photodynamic therapy, etc., is yet to become a common tool during the synthesis of small molecules in a laboratory. Among other rationale, the inability to influence photochemical reactions with temperature, solvent, additives, etc., dissuades chemists from employing light-initiated reactions as a routine synthetic tool. This review highlights how diverse, highly organized structures such as solvent-free crystals and water-soluble host–guest assemblies can be employed to control and manipulate photoreactions and thereby serve as an efficient tool for chemists, including those interested in synthesis. The efficacy of the media in modifying the excited-state behavior of organic molecules is illustrated with photocycloaddition in general and [2 + 2] photocycloaddition in particular, reactions widely employed in the synthesis of complex natural products as well as highly constrained molecules, as exemplars. The reaction media, highly pertinent in the context of green sustainable chemistry, include solvent-free crystals and solids such as silica, clay, and zeolite and water-soluble hosts that can solubilize and preorganize hydrophobic reactants in water. Since no other reagent would be more sustainable than light and no other medium greener than water, we believe that the supramolecular photochemistry expounded here has a momentous role as a synthetic tool in the future.