Regio- and stereodivergent antibiotic oxidative carbocyclizations catalysed by Rieske oxygenase-like enzymes.
Regio- and stereodivergent antibiotic oxidative carbocyclizations catalysed by Rieske oxygenase-like enzymes.
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氧化环化，例如从三肽前体生物合成青霉素核的组装，可以说是自然界中最具合成能力的C-H活化反应。在这里，我们表明，Rieske加氧酶样酶介导区域和立体分散氧化环化，形成10-和12-元碳环的抗生素链脲菌素B和metacycloprodigiosin的生物合成的关键步骤，分别。这些反应代表了由非血红素铁依赖性氧化酶催化的氧化碳环化的第一个例子，并定义了一种新型的Rieske酶的催化活性。更好地理解这些酶如何在未活化的烃链的官能化中实现如此显著的区域和立体控制，将极大地促进选择性人造C-H活化催化剂的开发。
Oxidative cyclizations, exemplified by the biosynthetic assembly of the penicillin nucleus from a tripeptide precursor, are arguably the most synthetically-powerful implementation of C-H activation reactions in Nature. Here we show that Rieske oxygenase-like enzymes mediate regio and stereodivergent oxidative cyclizations to form 10- and 12-membered carbocyclic rings in the key steps of the biosynthesis of the antibiotics streptorubin B and metacycloprodigiosin, respectively. These reactions represent the first examples of oxidative carbocyclizations catalyzed by non-heme iron-dependent oxidases and define a novel type of catalytic activity for Rieske enzymes. A better understanding of how these enzymes achieve such remarkable regio and stereocontrol in the functionalization of unactivated hydrocarbon chains will greatly facilitate the development of selective manmade C-H activation catalysts.
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影响因子：
56.9
作者：
Chen, Mark S.;White, M. Christina
通讯作者：
White, M. Christina
影响因子：
5.7
作者：
Kauppi, B;Lee, K;Ramaswamy, S
通讯作者：
Ramaswamy, S
影响因子：
3.3
作者：
Kawasaki, Takashi;Sakurai, Furni;Hayakawa, Yoichi
通讯作者：
Hayakawa, Yoichi
影响因子：
15
作者：
Liu, PH;Murakami, K;Liu, HW
通讯作者：
Liu, HW
DOI：
10.1039/c39870001736
发表时间：
1987-11-15
影响因子：
--
作者：
ELSON, SW;BAGGALEY, KH;WORONIECKI, SR
通讯作者：
WORONIECKI, SR