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Oxidative Cyclization in Natural Product Biosynthesis
Chemical Reviews ( IF 51.4 ) Pub Date : 2016-12-12 00:00:00 , DOI: 10.1021/acs.chemrev.6b00478 Man-Cheng Tang 1 , Yi Zou 1 , Kenji Watanabe 2 , Christopher T Walsh 3 , Yi Tang 1
Chemical Reviews ( IF 51.4 ) Pub Date : 2016-12-12 00:00:00 , DOI: 10.1021/acs.chemrev.6b00478 Man-Cheng Tang 1 , Yi Zou 1 , Kenji Watanabe 2 , Christopher T Walsh 3 , Yi Tang 1
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Oxidative cyclizations are important transformations that occur widely during natural product biosynthesis. The transformations from acyclic precursors to cyclized products can afford morphed scaffolds, structural rigidity, and biological activities. Some of the most dramatic structural alterations in natural product biosynthesis occur through oxidative cyclization. In this Review, we examine the different strategies used by nature to create new intra(inter)molecular bonds via redox chemistry. This Review will cover both oxidation- and reduction-enabled cyclization mechanisms, with an emphasis on the former. Radical cyclizations catalyzed by P450, nonheme iron, α-KG-dependent oxygenases, and radical SAM enzymes are discussed to illustrate the use of molecular oxygen and S-adenosylmethionine to forge new bonds at unactivated sites via one-electron manifolds. Nonradical cyclizations catalyzed by flavin-dependent monooxygenases and NAD(P)H-dependent reductases are covered to show the use of two-electron manifolds in initiating cyclization reactions. The oxidative installations of epoxides and halogens into acyclic scaffolds to drive subsequent cyclizations are separately discussed as examples of “disappearing” reactive handles. Last, oxidative rearrangement of rings systems, including contractions and expansions, will be covered.
中文翻译：
天然产物生物合成中的氧化环化
氧化环化是天然产物生物合成过程中广泛发生的重要转化。从无环前体到环化产物的转变可以提供变形的支架、结构刚性和生物活性。天然产物生物合成中一些最显着的结构改变是通过氧化环化发生的。在这篇综述中，我们研究了自然界通过氧化还原化学创建新的分子内（间）键的不同策略。本综述将涵盖氧化和还原环化机制，重点是前者。讨论了 P450、非血红素铁、α-KG 依赖性加氧酶和自由基 SAM 酶催化的自由基环化，以说明如何使用分子氧和S-腺苷甲硫氨酸通过单电子流形在未激活位点形成新键。涵盖了由黄素依赖性单加氧酶和 NAD(P)H 依赖性还原酶催化的非自由基环化，以展示双电子流形在引发环化反应中的使用。将环氧化物和卤素氧化安装到无环支架中以驱动随后的环化作为“消失”反应手柄的例子单独讨论。最后，将讨论环系统的氧化重排，包括收缩和扩张。
更新日期：2016-12-12
中文翻译：
天然产物生物合成中的氧化环化
氧化环化是天然产物生物合成过程中广泛发生的重要转化。从无环前体到环化产物的转变可以提供变形的支架、结构刚性和生物活性。天然产物生物合成中一些最显着的结构改变是通过氧化环化发生的。在这篇综述中，我们研究了自然界通过氧化还原化学创建新的分子内（间）键的不同策略。本综述将涵盖氧化和还原环化机制，重点是前者。讨论了 P450、非血红素铁、α-KG 依赖性加氧酶和自由基 SAM 酶催化的自由基环化，以说明如何使用分子氧和S-腺苷甲硫氨酸通过单电子流形在未激活位点形成新键。涵盖了由黄素依赖性单加氧酶和 NAD(P)H 依赖性还原酶催化的非自由基环化，以展示双电子流形在引发环化反应中的使用。将环氧化物和卤素氧化安装到无环支架中以驱动随后的环化作为“消失”反应手柄的例子单独讨论。最后，将讨论环系统的氧化重排，包括收缩和扩张。
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