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The Norrish reaction in organic chemistry describes the photochemical reactions taking place with ketones and aldehydes. This type of reaction is subdivided in Norrish type I reactions and Norrish type II reactions. The reaction is named after Ronald George Wreyford Norrish.
Contents
Type I
The Norrish type I reaction is the photochemical cleavage or homolysis of aldehydes and ketones into two free radical intermediates. The carbonyl group accepts a photon and is excited to a photochemical singlet state. Through intersystem crossing the triplet state can be obtained. On cleavage of the α-carbon bond from either state, two radical fragments are obtained. The size and nature of these fragments depends upon the stability of the generated radicals; for instance, the cleavage of 2-butanone largely yields ethyl radicals in favor of less stable methyl radicals.
Several secondary reaction modes are open to these fragments depending on the exact molecular structure.
The synthetic utility of this reaction type is limited, for instance it often is a side reaction in the Paternò–Büchi reaction. One organic synthesis based on this reaction is that of bicyclohexylidene.
Type II
A Norrish type II reaction is the photochemical intramolecular abstraction of a γ-hydrogen (a hydrogen atom three carbon positions removed from the carbonyl group) by the excited carbonyl compound to produce a 1,4-biradical as a primary photoproduct. Norrish first reported the reaction in 1937.
Secondary reactions that occur are intramolecular recombination of the two radicals to a substituted cyclobutane in the Norrish–Yang reaction, or fragmentation to an enol and an alkene.
Scope
The Norrish reaction has been studied in relation to environmental chemistry with respect to the photolysis of the aldehyde heptanal, a prominent compound in Earth's atmosphere. Photolysis of heptanal in conditions resembling atmospheric conditions results in the formation of 1-pentene and acetaldehyde in 62% chemical yield together with cyclic alcohols (cyclobutanols and cyclopentanols) both from a Norrish type II channel and around 10% yield of hexanal from a Norrish type I channel (the initially formed n-hexyl radical attacked by oxygen).
In one study the photolysis of an Acyloin derivative in water in presence of hydrogen tetrachloroaurate (HAuCl4) generated nanogold particles with 10 nanometer diameter. The species believed to responsible for reducing Au3+ to Au0 is the Norrish generated ketyl radical.
No fewer than three Norrish-type reactions feature in the classic 1982 total synthesis of dodecahedrane.
An example of a synthetically useful Norrish type II reaction can be found early in the total synthesis of the biologically active cardenolide ouabagenin by Baran and coworkers. The optimized conditions minimize side reactions, such as the competing Norrish type I pathway, and furnish the desired intermediate in good yield on a multi-gram scale.