Chemical synthesis and immunosuppressive activity of dipalmitoyl phosphatidylinositol hexamannoside

J Org Chem. 2011 Jun 17;76(12):4941-51. doi: 10.1021/jo200588u. Epub 2011 May 24.

Abstract

Phosphatidylinositol mannosides (PIMs) isolated from mycobacteria have been identified as an important class of phosphoglycolipids with significant immune-modulating properties. We present here the synthesis of dipalmitoyl phosphatidylinositol hexamannoside (PIM(6)) 1 and the first reported functional biology of a synthetic PIM(6). Key steps in the synthetic protocol included the selective glycosylation of an inositol 2,6-diol with a suitably protected mannosyl donor and construction of the glycan core utilizing a [3 + 4] thio-glycosylation strategy. The target 1 was purified by reverse phase chromatography and characterized by standard spectroscopic methods, HPLC, and chemical modification by deacylation to dPIM(6). The (1)H NMR spectrum of synthetic dPIM(6) obtained from 1 matched that of dPIM(6) obtained from nature. PIM(6) (1) exhibited dendritic cell-dependent suppression of CD8(+) T cell expansion in a human mixed lymphocyte reaction consistent with the well established immunosuppressive activity of whole mycobacteria.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Cell Differentiation
  • Cell Proliferation
  • Cells, Cultured
  • Humans
  • Lymphocyte Culture Test, Mixed
  • Molecular Structure
  • Phosphatidylinositols / chemical synthesis*
  • Phosphatidylinositols / immunology
  • T-Lymphocytes / cytology
  • T-Lymphocytes / immunology

Substances

  • Phosphatidylinositols
  • dipalmitoyl phosphatidylinositol hexamannoside
  • phosphatidylinositol mannoside