9.4 Formation of Carbon-Nitrogen Bonds

9.4.1 Barton Nitrite Photolysis Reaction

Photolysis of organic nitrites can be utilized to introduce functionality at unreactive aliphatic δ-carbon.

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For example, the synthesis of aldosterone 21-acetate from corticosterone acetate has been demonstrated.

Mechanism

Photolysis of organic nitrites gives oxy-radical which abstracts hydrogen from a δ-CH bond. The resulting alkyl radical reacts with nitric oxide liberated during the photolysis to yield a nitroso- derivative which tautomerizes to oxime that can be hydrolyzed to carbonyl group.