Toward mechanistic elucidation of iron acquisition in barley: efficient synthesis of mugineic acids and their transport activities

Iron acquisition of graminaceous plants is characterized by the synthesis and secretion of iron‐chelating compounds, mugineic acids (MAs), and by a specific uptake system for MAs‐iron(III) complexes. We identified a transporter, HvYS1 ( Hordeum vulgare L. yellow stripe 1), that is highly specific for MAs‐iron(III) in barley roots. In this article we outline the characterization of HvYS1, and our recent work on the practical syntheses of MAs and investigations into the molecular basis of the specific transport of their iron(III) complexes by HvYS1. 2′‐Deoxymugineic acid (DMA) was synthesized in a good overall yield from commercially available Boc‐l‐allylglycine using a minimal number of short simple operations with minimal protecting groups and work‐up/purification procedures. The same strategy was also successfully applied to β ‐hydroxy‐l‐allylglycine, which was obtained by an allylic oxidation of l‐allylglycine derivatives, to give MA and 2′‐epi‐MA efficiently. HvYS1 transported the iron(III) complexes of all three synthetic specimens with efficiency similar to that of a natural mugineic acid complex. With sufficient quantities of MAs in hand, we analyzed the function of HvYS1 and revealed by preparing chimeric transporters that the sixth outer membrane loop of the transporter plays a vital role in substrate specificity. © 2010 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 10: 140–150; 2010: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.200900028