渡環Diels-Alder反応を鍵とするツベラクトマイシンAの全合成研究

抄録

Tubelactomicins are tricyclic macrolide antibiotics, isolated from the culture broth of Nocardia sp., consisting of an octahydronaphthalene substructure with six contiguous stereogenic centers, and a 16-memberd lactone. We have explored the total synthesis of tubelactomicins by utilizing a biosynthesis-based transannular Diels-Alder (TADA) reaction as a key step.
The substrate for the macrocyclization reaction was synthesized by a multi-step sequence, including Horner-Wadsworth-Emmons reaction. The intramolecular Sonogashira coupling of this substrate proceeded at room temprature to give two TADA adducts, which might be produced after the Sonogashira reaction proceeded. Furthermore, this TADA reaction provided each an endo- and an exo-cycloadduct with excellent π-facial selectivity.

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