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Applications of Nonenzymatic Catalysts to the Alteration of Natural Products
Chemical Reviews ( IF 51.4 ) Pub Date : 2017-06-05 00:00:00 , DOI: 10.1021/acs.chemrev.7b00022 Christopher R Shugrue 1 , Scott J Miller 1
Chemical Reviews ( IF 51.4 ) Pub Date : 2017-06-05 00:00:00 , DOI: 10.1021/acs.chemrev.7b00022 Christopher R Shugrue 1 , Scott J Miller 1
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The application of small molecules as catalysts for the diversification of natural product scaffolds is reviewed. Specifically, principles that relate to the selectivity challenges intrinsic to complex molecular scaffolds are summarized. The synthesis of analogues of natural products by this approach is then described as a quintessential “late-stage functionalization” exercise wherein natural products serve as the lead scaffolds. Given the historical application of enzymatic catalysts to the site-selective alteration of complex molecules, the focus of this Review is on the recent studies of nonenzymatic catalysts. Reactions involving hydroxyl group derivatization with a variety of electrophilic reagents are discussed. C–H bond functionalizations that lead to oxidations, aminations, and halogenations are also presented. Several examples of site-selective olefin functionalizations and C–C bond formations are also included. Numerous classes of natural products have been subjected to these studies of site-selective alteration including polyketides, glycopeptides, terpenoids, macrolides, alkaloids, carbohydrates, and others. What emerges is a platform for chemical remodeling of naturally occurring scaffolds that targets virtually all known chemical functionalities and microenvironments. However, challenges for the design of very broad classes of catalysts, with even broader selectivity demands (e.g., stereoselectivity, functional group selectivity, and site-selectivity) persist. Yet, a significant spectrum of powerful, catalytic alterations of complex natural products now exists such that expansion of scope seems inevitable. Several instances of biological activity assays of remodeled natural product derivatives are also presented. These reports may foreshadow further interdisciplinary impacts for catalytic remodeling of natural products, including contributions to SAR development, mode of action studies, and eventually medicinal chemistry.
中文翻译：
非酶催化剂在天然产物改造中的应用
综述了小分子作为天然产物支架多样化催化剂的应用。具体来说，总结了与复杂分子支架固有的选择性挑战相关的原理。通过这种方法合成天然产物类似物被描述为典型的“后期功能化”练习，其中天然产物充当主要支架。鉴于酶催化剂在复杂分子的位点选择性改变方面的历史应用，本综述的重点是非酶催化剂的最新研究。讨论了涉及羟基衍生化与各种亲电子试剂的反应。还介绍了导致氧化、胺化和卤化的 C-H 键功能化。还包括位点选择性烯烃官能化和 C-C 键形成的几个例子。许多类别的天然产物都经过了这些位点选择性改变的研究，包括聚酮化合物、糖肽、萜类化合物、大环内酯、生物碱、碳水化合物等。出现的是一个对天然存在的支架进行化学重塑的平台，该平台几乎针对所有已知的化学功能和微环境。然而，设计非常广泛的催化剂类别以及更广泛的选择性要求（例如立体选择性、官能团选择性和位点选择性）仍然存在挑战。然而，复杂天然产物的一系列强大的催化改变现在已经存在，因此范围的扩大似乎是不可避免的。还介绍了重构天然产物衍生物的生物活性测定的几个实例。 这些报告可能预示着天然产物催化重塑的进一步跨学科影响，包括对 SAR 发展、作用模式研究以及最终药物化学的贡献。
更新日期：2017-06-05
中文翻译：
非酶催化剂在天然产物改造中的应用
综述了小分子作为天然产物支架多样化催化剂的应用。具体来说，总结了与复杂分子支架固有的选择性挑战相关的原理。通过这种方法合成天然产物类似物被描述为典型的“后期功能化”练习，其中天然产物充当主要支架。鉴于酶催化剂在复杂分子的位点选择性改变方面的历史应用，本综述的重点是非酶催化剂的最新研究。讨论了涉及羟基衍生化与各种亲电子试剂的反应。还介绍了导致氧化、胺化和卤化的 C-H 键功能化。还包括位点选择性烯烃官能化和 C-C 键形成的几个例子。许多类别的天然产物都经过了这些位点选择性改变的研究，包括聚酮化合物、糖肽、萜类化合物、大环内酯、生物碱、碳水化合物等。出现的是一个对天然存在的支架进行化学重塑的平台，该平台几乎针对所有已知的化学功能和微环境。然而，设计非常广泛的催化剂类别以及更广泛的选择性要求（例如立体选择性、官能团选择性和位点选择性）仍然存在挑战。然而，复杂天然产物的一系列强大的催化改变现在已经存在，因此范围的扩大似乎是不可避免的。还介绍了重构天然产物衍生物的生物活性测定的几个实例。 这些报告可能预示着天然产物催化重塑的进一步跨学科影响，包括对 SAR 发展、作用模式研究以及最终药物化学的贡献。
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