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. Author manuscript; available in PMC: 2013 Nov 7.
Published in final edited form as: J Am Chem Soc. 2012 Oct 26;134(44):18374–18379. doi: 10.1021/ja307315u

Scheme 1.

Scheme 1

Pre-steady state detection of forward rate constant for individual steps in DXP synthase catalytic cycle at 6 °C with both pyruvate and GAP present in LThDP formation.

k1 formation of LThDP; k2 is decarboxylation to enamine; k3 is carboligation with D-GAP to provide DXP~ThDP; k4 is release of DXP product. CD studies assume that LThDP and DXP~ThDP when bound to DXP synthase are both in the IP tautomeric form while NMR can differentiate them by the method of Tittmann et al.14 The decarboxylation rate constant 4.2 × 101 s−1 pertains to k2.