Study of asymmetric total synthesis of nakadomarin A

点击翻译按钮获取中文摘要

We completed the total synthesis of (+)-nakadomarin in a highly stereoselectve manner from the commercially available L-pyroglutamic acid. The most significant point of this synthesis involves the intramolecular Pauson-Khand reaction between the alkyne and N-protected-dihydropyrrole functionalities, which enabled us to construct the diazatricyclo[6.4.0.0^<1,5>]dodcadienone product. This reaction was also useful for the short-step synthesis of (±)-meloscine. In addition, we succeeded to extend the application of the rhodium catalyzed Pauson-Khand type reaction of allenenes for the construction of bicyclo[4.3.0] skeletons containing quaternary carbon at the ring juncture. This method provided a new procedure for the construction of the tricyclo[6.4.0.0^<1,5>]dodecenone framework in a satisfactory yield.