We found a match
Your institution may have access to this item. Find your institution then sign in to continue.
- Title
Enantioselective Total Synthesis of Hyperforin and Pyrohyperforin.
- Authors
Ji, Yunpeng; Hong, Benke; Franzoni, Ivan; Wang, Mengyang; Guan, Weiqiang; Jia, Hongli; Li, Houhua
- Abstract
Capitalizing on the late‐stage diversification of an essential 1,3‐diene intermediate, we describe herein a 9‐step enantioselective total synthesis of (+)‐hyperforin and (+)‐pyrohyperforin, starting from commercially available allylacetone. Our convergent synthesis features a series of critical reactions: 1) an enantioselective deconjugative α‐alkylation of α,β‐unsaturated acid using chiral lithium amides as noncovalent stereodirecting auxiliaries; 2) a HfCl4‐mediated carbonyl α‐tert‐alkylation to forge the intricate bicyclo[3.3.1]nonane framework; 3) an abiotic cascade pyran formation; and 4) a selective 1,4‐semihydrogenation of polyenes. During the course of our synthesis, we also identified a 1,2‐cyclopropanediol overbred intermediate which was responsible for the 1,3‐diene precursor formation through a controlled fragmentation.
- Subjects
PYRAN; AMIDES; POLYENES; NATURAL products; DIOLEFINS
- Publication
Angewandte Chemie, 2022, Vol 134, Issue 16, p1
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.202116136