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Synthesis of potential inhibitors of early stages in the shikimate pathway
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Synthesis of potential inhibitors of early stages in the shikimate pathway
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Synthesis of potential inhibitors of early stages in the shikimate pathway
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Dissertation
Synthesis of potential inhibitors of early stages in the shikimate pathway
1993
Overview
The synthesis is reported of some analogues of 3-deoxy-D-arabino-heptulosonic acid 7-phosphate (DAHP,3) an intermediate in the Shikimate pathway, and of some analogues of 3-deoxy- -D-arabino-heptulosonic acid 2,7-diphosphate (167), the intermediacy the existence of which is proposed in this thesis in a new alternative mechanism for the enzymic reaction catalysed by DAHP synthase. 2-Deoxy- - and - -D-arabino-hexopyranosyl-phosphonic acids (169) and (168) were synthesised in high yield from 2-deoxy-D-glucose (69). Acetylation of (69) in acetic anhydride and pyridine gave 1,3,4,6-tetra-O-acetyl-2-deoxy- , -D-arabino-hexopyranose (23 , ) which was then treated with trimethyl phosphite and trimethylsilyl triflate to give dimethyl (3,4,6-tri-O-acetyl-2-deoxy- - and - -D-arabino-hexopyranosyl)-phosphonates (180) and (181). These were deprotected with trimethylsilyl bromide followed by sodium methoxide in methanol to give the phosphonic acids (169) and (168). A stereospecific synthesis to give a protected form of (169) was also carried out. Tri-O-benzyl-D-glucal (80) was treated with hydrogen chloride gas in toluene followed by lithio tributylstannylate to give specifically tributyl (3,4,6-tri-O-benzyl-2-deoxy- -D-arabino-hexopyranosyl)stannane (204). Transmetallation with butyllithium followed by reaction with diethyl chlorophosphate then gave diethyl (3,4,6-tri-O-benzyl-2-deoxy- -D-arabino-hexopyranosyl)-phosphonate (208). As an alternative 3,4,6-tri-O-t-butyldiphenylsilyl-D-glucal (228) was synthesised from D-glucal (176) and was treated with t-butyllithium followed by diethyl chlorophosphate to give diethyl (tri-O-t-butyldiphenylsilyl-2-deoxy-D-arabino-hex-1-enopyranosyl)-phosphonate (229). An attempt to hydrogenate this specifically to give a protected -phosphonate was unsuccessful. (DX179064)
Publisher
ProQuest Dissertations & Theses
Subject
