Approaches toward synthesis of the mycosporins Public Deposited

http://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/z316q603s

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  • The mycosporins, formerly called P310's are secondary metabolites of fungi closely associated with fungal reproductive processes that require light. The structurally related iminomycosporins are found in marine plants and animals and may also have functions related to light. In this study, approaches toward the asymmetric synthesis of the mycosporins are presented. Methodology was developed around refunctionalization of D-(-)-quinic acid (35) in which the secondary hydroxy groups were differentiated, independently modified, and oxidized to the mycosporin oxidation level. Protection of (1R,2S13R15R)-1,2-0-cyclopentylidene-1,2,315- tetrahydroxy-5-hydroxymethylcyclohexane (39) and (1S,3R,4R,5R)-1,3,4- trihydroxy-6-oxabicyclo[3.2.1]octan-7-one (56), both derived from D-quinic acid, were pursued. An approach was utilized in which D-quinic acid was lactonized and protected to form (1S,3R,41215R)-314-0-benzylidene-11314-trihydroxy- 6-oxabicyclo[3.2.1]octan-7-one (61). Selective bromination with N-bromosuccinimide, reduction, and diol protection gave a mixture of a- and ,8-bromo alcohols, 79 and 80, which were oxidized to their respective ketones (81 and 89). Transformation of a-bromo ketone, 89, to a-hydroxy ketone 104 occurred in aqueous potassium carbonate. Conversion of 89 to a-hydroxy ketal 100 with potassium carbonate in methanol and subsequent oxidation with pyridinium chlorochromate yielded the protected a-diketone, (3R15R)-3-benzoyloxy-5-hydroxy-5- hydroxymethy1-2,2-dimethoxycyclohexanone (100), at the target oxidation level.
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  • 1986
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