Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 53, Issue 16, Pages 4217-4221Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201400605
Keywords
alkyne metathesis; molybdenum; natural products; structure elucidation; total synthesis
Categories
Funding
- MPG
- Fonds der Chemischen Industrie (Kekule stipend)
Ask authors/readers for more resources
A concise synthesis of the putative structure assigned to the highly cytotoxic marine macrolide mandelalideA (1) is disclosed. Specifically, an iridium-catalyzed two-directional Krische allylation and a cobalt-catalyzed carbonylative epoxide opening served as convenient entry points for the preparation of the major building blocks. The final stages feature the first implementation of terminal-acetylene metathesis into natural product synthesis, which is remarkable as this class of substrates was beyond reach until very recently; key to success was the use of the highly selective molybdenum alkylidyne complex 42 as the catalyst. Although the constitution and stereochemistry of the synthetic samples are unambiguous, the spectra of 1 as well as of 11-epi-1 deviate from those of the natural product, which implies a subtle but deep-seated error in the original structure assignment.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available