The observation of remarkable effects of remotely connected but spatially proximate hydroxy-groups on the rates and regiochemistry of the birch reduction of aromatic rings and double bonds

Cotsaris, E.; Paddon‐Row, Michael N.

doi:10.1039/p29840001487

Cited by 9 publications

(1 citation statement)

References 18 publications

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“…Alcohol (42), however, is (40) (45) Scheme 4 (43) (46) reduced within minutes to the tetrahydro product (46), which arises through protonation at substituted positions on the more hindered face of the aromatic ring and is therefore clearly intramolecular in nature. 30 During a total synthesis of the diterpenoid enmein, the tricyclic alcohols (47) and (48) were converted into a range of c-ring ketones (Scheme 5). 30 During a total synthesis of the diterpenoid enmein, the tricyclic alcohols (47) and (48) were converted into a range of c-ring ketones (Scheme 5).…”

Section: Intramolecular Protonation Ofbirch Intermediatesmentioning

confidence: 99%

Partial Reduction of Aromatic Rings by Dissolving Metals and by Other Methods

Mander

1991

Comprehensive Organic Synthesis

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Section: Intramolecular Protonation Ofbirch Intermediatesmentioning

confidence: 99%

Partial Reduction of Aromatic Rings by Dissolving Metals and by Other Methods

Mander

1991

Comprehensive Organic Synthesis

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TheBirch Reduction of Aromatic Compounds

Rabideau

Marcinow²

1992

Organic Reactions

134

138

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The reduction of aromatic compounds by alkali metals in liquid ammonia represents an important method for the preparation of partially unsaturated six‐membered rings. The reaction was discovered by Wooster and Godfrey, but the major development resulted from the efforts of A. J. Birch, and the reaction has since come to bear his name. Although a variety of metals can be used, the most common are sodium and lithium, and, to a lesser extent, potassium. Cosolvents such as ether or tetrahydrofuran (THF) are often used to improve solubility, and weak acids such as alcohols may be employed during the reaction as proton sources. The latter are necessary for the reduction of benzene and its unactivated derivatives. Improvement in experimental procedures by Wilds and Nelson, the application to polynuclear compounds by Hückel and later by Harvey, and the development of methods for the alkylation of the anions generated in this process (i.e., reductive alkylation) have made this reaction an important approach to the synthesis of a wide variety of organic compounds.

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Birch Reduction

2010

Comprehensive Organic Name Reactions and Reagents

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The reduction of aromatic compounds by alkali metal in liquid ammonia in the presence of alcohol is generally known as the Birch reduction or metal‐ammonia reduction. The Birch reduction uses the ammonia‐solvated electrons arising from alkali metal as the reducing agent, which bears the extremely negative single‐electron redox potential. Once the solvated electron adds to aromatic system, the radical anion is quenched by alcohol, so that cyclohexa‐1,4‐diene derivatives are often produced from benzene derivatives without further reduced species. It has been pointed out that the existing alkali metal also reacts with alcohol to generate hydrogen, in a reaction known as the hydrogen reaction. It has been reported that both the rate and yield of the Birch reduction decreases in the order of Li>Na>K. One of the advantages associated with the Birch reduction is its efficient steric control on the aromatic system. The applications of the Birch reduction are to convert aryl alkyl ethers into 1‐alkoxycyclohexa‐1,4‐dienes and also to reduce acetylenes stereospecifically to trans‐olefins and to hydrogenate graphite and carbon single‐walled nanotubes (SWNTs). The Birch reaction has also been found to cleave the CC bond in the presence of the aromatic system.

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The observation of remarkable effects of remotely connected but spatially proximate hydroxy-groups on the rates and regiochemistry of the birch reduction of aromatic rings and double bonds

Cited by 9 publications

References 18 publications

Partial Reduction of Aromatic Rings by Dissolving Metals and by Other Methods

Partial Reduction of Aromatic Rings by Dissolving Metals and by Other Methods

TheBirch Reduction of Aromatic Compounds

Birch Reduction

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