Department of Chemistry , Indian Institute of Technology Bombay , Powai, Mumbai 400076 , Maharashtra , India.
Org Lett. 2019 Aug 2;21(15):5827-5831. doi: 10.1021/acs.orglett.9b01897. Epub 2019 Jul 17.
An efficient total synthesis of the revised structure of the sensitive triyne natural product, (4,5)-4,8-dihydroxy-3,4-dihydrovernoniyne, and all of its stereoisomers, that is, the previously proposed (4,5), (4,5), and (4,5), has been accomplished from chiral pool compounds l-mannonic-γ-lactone and d-glucono-δ-lactone. The key features involve a one-pot conversion of the chiral pool compounds into the γ-vinyl-β-hydroxy-γ-lactones, the heteroatom-directed Wacker oxidation, the Seyferth-Gilbert reaction, and Cadiot-Chodkiewicz coupling. The synthesis also involves minimal protecting groups (only -butyldimethylsilyl) and is completed in seven to eight steps.
从手性池化合物 L-甘露酸γ-内酯和 D-葡萄糖酸δ-内酯出发，高效地完成了对敏化三炔天然产物（4,5）-4,8-二羟基-3,4-二氢 vernoniyne 的修订结构及其所有立体异构体（4,5）、（4,5）和（4,5）的全合成。关键特点包括手性池化合物一锅转化为γ-乙烯基-β-羟基-γ-内酰胺、杂原子导向的 Wacker 氧化、Seyferth-Gilbert 反应和 Cadiot-Chodkiewicz 偶联。该合成还涉及最小的保护基（仅叔丁基二甲基甲硅烷基），并在七到八个步骤中完成。
