Luminmycin A

Luminmycin A, a natural proteasome inhibitor transcripted by a silent gene cluster from Photorhabdus luminescens, belongs to the compound family of the syrbactins and glidobactins. Müller et al. were able to express silent megasynthetase gene clusters from Photorhabdus luminescens in heterologous hosts and elucidated the biochemical pathway of the luminmycins.

  • J. Fu, X. Y. Bian, S. B. Hu, H. L. Wang, F. Huang, P. M. Seibert, A. Plaza, L. Q. Xia, R. Müller, A. F. Stewart, Y. M. Zhang, Nature Biotech. 2012, 30, 440–446.
 

Key step for the synthesis of the 12-membered cyclopeptide ring is an intramolecular Horner-Wadsworth-Emmons reaction, while the double unsaturated fatty acid side chain can be obtained via phosphine-catalyzed isomerization of a corresponding acetylenic fatty acid ester.

  • P. Servatius, T. Stach, U. Kazmaier, "Total synthesis of luminmycin A, a cryptic natural product from Photorhabdus luminescens", Eur. J. Org. Chem. 2019, 3163–3168.