Natural Products Chemistry Division and ‡Centre for NMR and Structural Chemistry, CSIR-Indian Institute of Chemical Technology , Hyderabad 500007, India.
Org Lett. 2017 Aug 18;19(16):4167-4170. doi: 10.1021/acs.orglett.7b01620. Epub 2017 Aug 1.
The first asymmetric total synthesis of two possible diastereomers (4S,5R)-4,8-dihydroxy-3,4-dihydrovernoniyne 5 and (4S,5S)-4,8-dihydroxy-3,4-dihydrovernoniyne 5a is accomplished. Salient features of the synthesis involve Cadiot-Chodkiewicz coupling and Sonogashira cross-coupling of terminal acetylenes. Detailed comparison of the H and C NMR data and specific rotation with that of the natural product led to the revision of the absolute stereochemistry of the natural product as (4S,5S)-4,8-dihydroxy-3,4-dihydrovernoniyne 5a.
（4S,5R）-4,8-二羟基-3,4-二氢 vernoniyne 5 和（4S,5S）-4,8-二羟基-3,4-二氢 vernoniyne 5a 的两种可能非对映异构体的首次不对称全合成已经完成。合成的显著特点包括末端炔烃的 Cadiot-Chodkiewicz 偶联和 Sonogashira 交叉偶联。与天然产物的 1H 和 13C NMR 数据和比旋光度的详细比较导致对天然产物的绝对立体化学进行了修订，确定其为（4S,5S）-4,8-二羟基-3,4-二氢 vernoniyne 5a。
