Total synthesis enabled structure revision of sesquiterpenoids

Sesquiterpenoids have attracted the attention of chemists and biologists due to their unique structures and potential biological activities. Because of the complexity of their structures, many sesquiterpenoids have not been accurately assigned in the initial isolation and identification process, which caused obstacles to following research. In this mini-review, we systematically summarized the structural revision of sesquiterpenoids based on the total synthesis reported from 2016 to 2024. The discussion is categorized into four aspects based on different strategies of structural revision: (1) re-evaluation based on NMR analysis or computational simulations; (2) discrepancy in optical rotation values; (3) confirmation via X-ray crystallography; (4) synthesis and comparison of optical isomers. On the one hand, the review fills the gap of structural revision of sesquiterpenoids based on total synthesis. On the other hand, it also provides synthetic chemists with critical insights into the powerful applications and distinct perspectives of total synthesis approaches in the structural elucidation and revision of natural products.