Asymmetric total syntheses of (+)- and (-)-versicolamide B and biosynthetic implications.
Asymmetric total syntheses of (+)- and (-)-versicolamide B and biosynthetic implications.
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Diels-Alder反应是研究得最充分、合成上最有用的有机转化之一。虽然大量天然存在的物质被认为是由生物合成的Diels-Alder反应产生的，但严格确认一种机械上独特的天然Diels-Alderase酶仍然难以捉摸。在这种情况下，曲霉属内的几种相关真菌产生许多绝对构型相反的代谢物，包括(+)-或(−)-versicolamide B.这些生物碱被假设通过生物合成Diels-Alder反应产生，这意味着每种曲霉都具有不同的diels - alderase。本文描述了通过部署IMDA反应作为(+)-和(−)-versicolamide B不对称全合成的关键步骤，对这些生物合成建议进行实验验证。实验室验证了所提出的生物合成Diels-Alder结构，加上产生真菌的次级代谢物谱，表明每个曲霉菌物种都进化出了对映体不同的吲哚氧化酶，以及对映体不同的diels - alderase。
The Diels-Alder reaction is one of the most well-studied, synthetically useful organic transformations. While a significant number of naturally occurring substances are postulated to arise by biosynthetic Diels-Alder reactions, rigorous confirmation of a mechanistically distinct natural Diels-Alderase enzyme remains elusive. Within this context, several related fungi within the Aspergillus genus produce a number of metabolites of opposite absolute configuration including (+)- or (−)-versicolamide B. These alkaloids are hypothesized to arise via biosynthetic Diels-Alder reactions implying that each Aspergillus species possesses enantiomerically distinct Diels-Alderases. Herein, experimental validation of these biosynthetic proposals via deployment of the IMDA reaction as a key step in the asymmetric total syntheses of (+)- and (−)-versicolamide B is described. Laboratory validation of the proposed biosynthetic Diels-Alder construction, coupled with the secondary metabolite profile of the producing fungi, reveals that each Aspergillus species has evolved enantiomerically distinct indole oxidases, as well as enantiomerically distinct Diels-Alderases.
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影响因子：
3.6
作者：
Domingo, LR;SanzCervera, JF;Marco, JA
通讯作者：
Marco, JA
影响因子：
2.1
作者：
Greshock, Thomas J.;Grubbs, Alan W.;Williams, Robert M.
通讯作者：
Williams, Robert M.
Notoamides A-D:: 从一种源自海洋的真菌 Aspergillus sp.
影响因子：
16.6
作者：
Kato, Hikaru;Yoshida, Takushi;Tsukamoto, Sachiko
通讯作者：
Tsukamoto, Sachiko
DOI：
10.1039/c2970001103a
发表时间：
1970-01-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY D-CHEMICAL COMMUNICATIONS
影响因子：
--
作者：
PORTER, AEA;SAMMES, PG
通讯作者：
SAMMES, PG
影响因子：
2.1
作者：
TSUDA, M;KAWASAKI, N;KOBAYASHI, J
通讯作者：
KOBAYASHI, J