A Cope Rearrangement in the Reaction Catalyzed by Dimethylallyltryptophan Synthase?
A Cope Rearrangement in the Reaction Catalyzed by Dimethylallyltryptophan Synthase?
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DOI：
10.1021/ja2034969
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发表时间：
2011-08-17
影响因子：
15
通讯作者：
Tanner, Martin E.
中科院分区：
文献类型：
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作者：
Luk, Louis Y. P.;Qian, Qj;Tanner, Martin E.
二甲基烯丙基色氨酸合酶催化麦角生物碱生物合成第一步中的C-4位的TIP的“正常”异戊二烯化。发现Lys 174 Ala突变体产生六氢吡咯并吲哚生物碱，其主要产物是C-3处的“反向异戊二烯化”。这被解释为支持一种机制的证据，该机制涉及C-3的初始“反向异戊二烯化”，随后是科普重排和rearomatization。
The enzyme dimethylallyltryptophan synthase catalyzes the "normal" prenylation of Tip at C-4 in the first step of ergot alkaloid biosynthesis. The Lys174Ala mutant is found to produce a hexahydropyrroloindole alkaloid that is "reverse-prenylated" at C-3 as its major product. This is interpreted as evidence in support of a mechanism that involves an initial "reverse-prenylation" at C-3, followed by a Cope rearrangement and rearomatization.