Cristau Pierre, Temal-Laïb Taoues, Bois-Choussy Michèle, Martin Marie-Thérèse, Vors Jean-Pierre, Zhu Jieping
Institut de Chimie des Substances Naturelles, CNRS, 91198 Gif-sur-Yvette Cedex, France.
Chemistry. 2005 Apr 22;11(9):2668-79. doi: 10.1002/chem.200401070.
A unified strategy for the synthesis of mauritines A (5), B (6), C (7), and F (10) has been developed based on a key intramolecular nucleophilic aromatic substitution reaction (S(N)Ar) for the formation of the strained 14-membered paracyclophane. It was demonstrated that the outcome of the cycloetherification is independent of the stereochemistry of the peptide backbone and that both (1R)-16 and (1S)-16 cyclized smoothly to provide the corresponding macrocycle. On the other hand, dehydration of the secondary benzylic alcohol, via the phenylselenide intermediate, is configuration dependent. (1R)-25 underwent the two-step syn-elimination much more easily than (1S)-22. A modified reductive deamination procedure via the diazonium intermediate was developed. A complete assignment of proton and carbon NMR spectroscopy signals for these natural products is reported for the first time.
基于关键的分子内亲核芳香取代反应（S(N)Ar）以形成张力14元对环芳烷，已开发出一种用于合成毛里求斯菌素A（5）、B（6）、C（7）和F（10）的统一策略。结果表明，环醚化的结果与肽主链的立体化学无关，并且（1R）-16和（1S）-16均能顺利环化以提供相应的大环。另一方面，通过苯硒化物中间体进行的仲苄醇脱水反应取决于构型。（1R）-25比（1S）-22更容易进行两步顺式消除反应。开发了一种通过重氮中间体的改进还原脱氨程序。首次报道了这些天然产物的质子和碳核磁共振光谱信号的完整归属。
