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-Selenoaldehydes
Hydrogenolysis of carbon-selenium bonds Selenium() reagents find use as oxidizing agents
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General features
A multitalented element: selenium reagents offer numerous possibilities in organic synthesis
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Selenoxide can be obtained by oxidation of corresponding selenide. The oxidants may be hydrogen peroxide, peroxy acids, sodium periodate and ozone.
Selenoxides with a -hydrogen can readily undergo thermal eliminationreaction to generate alkene.
Using this procedure, we can achieve conversion of ketones to enones and synthesis of allylic alcohols. The variants of the procedure is in the preparation of the selenide rather than in the oxidation-elimination stage.
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Preparation of selenides
From an electrophilic selenium reagent and a carbon nucleophile. From a nucleophilic selenium reagent and a carbon electrophile From a simpler selenid
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Example
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For synthesis of allylic alcohols, the overall reaction amounts to an allylic oxidation, with a rearrangement of the double bond. Selenide from addition of aryselenenyl halide to alkene can also react with nucleophilic functional groups. For alkenes containing suitably positioned nucleophilic functional groups may undergo cyclization.
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Lithium in ethylamine
Triphenyltin() hydride, Ph3SnH: expensive and air sensitive Nickel boride, produced in situ by reaction of nickel chloride and sodium borohydride.
Synthetic applications:
Reductive alkylation of aldehydes and ketones Formation of reduced heterocycles Oxidation of alkenes to ketones
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Summary
Alcohols are converted into alkyl aryl selenides by reaction with aryl selenocyanates, ArSeCN. These react with bromine in the presence of a base, giving alkyl bromides: the overall reaction is ROH RBr with retention of configuration. Aryl alkyl selenides are preparable either (as above) from electrophilic selenium reagents and carbon ncleophiles or from nucleophilic selenium reagents, e.g. ArSe-Na+, and carbon electrophiles. On oxidation they give selenoxides; if these contain a -hydrogen, they may undergo spontaneous syn-addition at ambient temp. to give alkenes. Allyl selenoxides undergo rearrangement to allyl selenenates, which are hydrolysable to allylic alcohols.
-selenoaldehydes undergo condensation reactions, and a double bond may then be introduced in the product by oxidation at the selenium atom followed by elimination.
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