Jump to main content
Jump to site search

Issue 21, 2006
Previous Article Next Article

Studies in sigmatropic rearrangements of N-prenylindole derivatives – a formal enantiomerically pure synthesis of tryprostatin B

Author affiliations

Abstract

Rearrangement of Na-prenyl-Nb-acetyltryptamine, induced by BF3·Et2O at low temperature, leads to a 2-prenyl derivative, and thence to the tricyclic tryptamine 7 and the indoline 8. Similarly, Na-prenyl-Nb-phthaloyl-L-tryptophan methyl ester furnished the corresponding 2-prenyl derivative 16, a known advanced precursor of tryprostatin B. Density functional (B3LYP) calculations for the putative rearrangement transition state for N-prenylskatole show that prior coordination of BF3 to the indolic nitrogen changes the character of the subsequent sigmatropic pericyclic shifts from being entirely covalent to acquiring a significant degree of ionic character. The shifting prenyl group favours the endo over the exo mode of the transition state by 4.1 kcal mol−1.

Graphical abstract: Studies in sigmatropic rearrangements of N-prenylindole derivatives – a formal enantiomerically pure synthesis of tryprostatin B

Back to tab navigation

Supplementary files

Publication details

The article was received on 22 May 2006, accepted on 12 Sep 2006 and first published on 28 Sep 2006


Article type: Paper
DOI: 10.1039/B606457D
Citation: Org. Biomol. Chem., 2006,4, 3966-3972
  •   Request permissions

    Studies in sigmatropic rearrangements of N-prenylindole derivatives – a formal enantiomerically pure synthesis of tryprostatin B

    A. S. P. Cardoso, M. M. B. Marques, N. Srinivasan, S. Prabhakar, A. M. Lobo and H. S. Rzepa, Org. Biomol. Chem., 2006, 4, 3966
    DOI: 10.1039/B606457D

Search articles by author

Spotlight

Advertisements