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Synthesis of linalool and limonene sensitizing hydroperoxides ! E - - PowerPoint PPT Presentation
Synthesis of linalool and limonene sensitizing hydroperoxides ! E - - PowerPoint PPT Presentation
Synthesis of linalool and limonene sensitizing hydroperoxides ! E Gimnez-Arnau Laboratoire de Dermatochimie Institut de Chimie de Strasbourg Universit de Strasbourg (CNRS-UMR 7177) Strasbourg, France Methods to prepare hydroperoxides
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Non-selective, multitude of oxidation products … !
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Methods to prepare hydroperoxides
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Methods to prepare hydroperoxides
Singlet oxygen ene reaction – Schenck reaction!
production of singlet oxygen! f i Photochemical methods : mostly employed!
Bengal Rose! Methylene Blue!
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Methods to prepare hydroperoxides
Singlet oxygen ene reaction – Schenck reaction!
Chemical methods: peroxomolybdates intermediates!
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Methods to prepare hydroperoxides
Schenck reaction on trisubstituted olefins!
regioselectivity and stereoselectivity
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Methods to prepare hydroperoxides
Nucleophilic substitution on allylic alcohols !
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Hydroperoxides of our concern
Lin-7-OOH! Lim-2-OOH!
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Synthesis of Lin-7-OOH
Experimental conditions : obtention of 1O2
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Schenck reaction on trisubstituted olefin!
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Synthesis of Lin-7-OOH
Experimental conditions : microemulsion
Schenck reaction on trisubstituted olefin!
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Synthesis of Lin-7-OOH
Mixture of hydroperoxides TBDPSCl Imidazole DMF 391 mg 1,2 éq. 2 éq. 8,5 mL Two isomers protected 200 mg 1,2 éq. 2 éq. 8,5 mL One single isomer protected
Chemical derivatization (silylization) of the hydroperoxides!
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Synthesis of Lin-7-OOH
Deprotection of the peroxysilane!
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Synthesis of Lin-7-OOH
Derivatization/Deprotection optimization!
Weight mixture hydroperoxides Concentration mixture hydroperoxides Reaction time Yield on the last two steps 200 mg 0,13 mol.L-1 2 days 13% 200 mg 0,11 mol.L-1 10 days 61% 200 mg 0,14 mol.L-1 10 days 59% 200 mg 0,21 mol.L-1 10 days 96% 1 g 0,21 mol.L-1 10 days 9%
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Synthesis of Lin-7-OOH
Summary!
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Synthesis of Lim-2-OOH
First tests! Schenck reaction SN2 nucleophilic substitution
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Synthesis of Lim-2-OOH
SN1 nucleophilic substitution!
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