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Chapter 14 Selenium reagents

Functional group interconversion: alcohols into bromide


syn-Elimination from selenoxides Allylic selenoxide and selenide

-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

Commercially available selenium reagents including:


Potassium selenocyanate, KSeCN Areneselenols, ArSeH Diary diselenides, ArSeSeAr Areneselenyl halides, ArSeX (X = Cl, Br or I)
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Functional group interconversion: alcohols into bromide

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syn-Elimination from selenoxides

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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Conversion of Carbonyl compounds to ,-unsaturated

Carbonyl compounds by Selenoxide Syn Elimination

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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Preparation of allylic alcohols and -halogenoalkenes by


selenoxide syn-elimination
Preparation of selenide
From addition of benzeneselenenic acid to alkene. From addition of arylselenenyl halide to alkene.

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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Unimolecular syn-Eliminations ( Pyrolytic syn-elimination)

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Allylic selenoxide and selenide


Preparation of allylic selenides
Reaction of an allyl halide with a selenide anion

Alkylation of an allylselenide anion


By a wittig reaction

The allyl selenoxide rearrangement

Reaction with trialkylboranes: synthesis of -hydrogen alkene

Reaction with alkyl-lithium reagents: selenium-lithium exchange


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Hydrogenolysis of carbon-selenium bonds


Reagents for hydrogenolysis of carbon-selenium bonds
Raney nickel

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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Selenium() reagents find use as oxidizing agents


Selenium dioxide as oxidizing reagent
Ketones containing an -methyllene are oxidized to diketones Elimination of 1,2,3-Selenadiazole

Oxidation using benzeneseleninic acid


Oxidation using benzeneseleninic anhydride

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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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Allylic selenides are convertible into allyl-lithium reagents for further


reactio with electrophiles. Hydrogenolysis of carbon-selenium bonds is achievable using catalytic methods, dissolving metals, triaryltin hydrides and nickel boride. 1,2,3-Selenadiazole undergo elimination, giving alkynes, either on heating or treatment with organolithium reagents. Highly reactive cycloalkynes are preparagble in this way. Selenium() reagents find use as oxidizing agents, such as selenium() oxide, benzeneseleninic acid (in combination with hydrogen peroxide) and benzeneseleninic anhydride.

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