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Figure 1.
Figure 1. (a) R = OdTDP. The RmlC reaction converts
dTDP-6-deoxy-D-xylo-4-hexulose to dTDP-6-deoxy-L-lyxo-4-hexulose
(thick arrow). This process involves a ring flip as well as
epimerization. The steps are shown according to the current
convention, however, this route goes through some very high
energy intermediates (notably the C1′, C3′, C5′ triaxial
product). (b) R = OGPD. The GME reaction converts GDP-D-mannose
to GDP-L-galactose. Shown boxed is the predicted twist boat
intermediate. The dominant order of the epimerization (C5′
first) and the ring flipped form of GDP-L-ribo-4-hexulose were
determined experimentally.^24 (c) R = OdTDP. Substrate and
product mimics employed in this study.
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