Asymmetric Total Synthesis of Chaetoglobin A.

J Org Chem

Department of Chemistry, Roy and Diana Vagelos Laboratories, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.

Published: June 2023

An asymmetric total synthesis of chaetoglobin A was achieved. Atroposelective oxidative coupling of a phenol incorporating all but one carbon of the final product was used as a key step to generate axial chirality. The stereochemical outcome of the catalytic oxidative phenolic with the highly substituted phenol used herein was found to be opposite that of the simpler congeners reported previously, providing a cautionary tale about extrapolating asymmetric processes from simple to more complex substrates. Optimization of the postphenolic coupling steps including formylation, oxidative dearomatization, and selective deprotection steps are outlined. The tertiary acetates of chaetoglobin A were exceptionally labile due to activation by the adjacent keto groups, which complicated each of these steps. In contrast, the final oxygen to nitrogen exchange proceeded readily and the spectroscopic data from the synthetic material matches that of the isolated natural product in all respects.

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Source
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC10411588PMC
http://dx.doi.org/10.1021/acs.joc.3c00002DOI Listing

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