Reduction of benzene nucleus with magnesium and alcohol in liquid ammonia

Markov, P.; Ivanoff, Christo

doi:10.1016/s0040-4039(00)70975-0

Cited by 12 publications

(11 citation statements)

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“…film): 3020, , 1028 (7). To a solution of 6.24 g (41.6 mmol) of the spiro [4,5]dec-6en-I-one (6) and 16.9 ml ( 5 mol-equiv.) of pyridine in 12 ml of abs.…”

Section: Aikylation Of Ethyl 2-cyclohexen-l-carboxylate (3)mentioning

confidence: 99%

“…-IR. (CHC13): 3580, 3265, 2995, 2935, 2860, 2840, 1665 br, 1443, 1420, 1352, 1178, 950, 926, 906, 869 148,146,133,131,120,119,107,91,79 0-Benzylation ofspiro [4,5]dec-6-en-l-one oxime (7). To a suspension of 229 mg (1.2 mol-equiv.)…”

Section: Aikylation Of Ethyl 2-cyclohexen-l-carboxylate (3)mentioning

confidence: 99%

“…To a suspension of 229 mg (1.2 mol-equiv.) of K H in 20 ml of dry DME at 0" was added a solution of 785 mg (4.76 mmol) of spiro [4,5]dec-6-en-1-one oxime (7) in 10 ml of dry DME. After stirring the reaction mixture for 15 min at 0" (evolution of hydrogen had stopped) 0.68 ml (1.2 mol-equiv.)…”

Section: Aikylation Of Ethyl 2-cyclohexen-l-carboxylate (3)mentioning

confidence: 99%

“…A solution of 1.06 g (4.16 mmol) of the 0-benzylether of spiro [4,5]dec-6-en-l-one oxime 8 in 100 ml of DME and 50 ml of water was treated with 1.11 g (1.5 mol-equiv.) of N-bromosuccinimide at -20".…”

Section: Spiro[45]dec-6-en-z-one Oximementioning

confidence: 99%

“…Subsequent hydrolysis-decarboxylation gave after distillation spiro [4,5]dec-6-en-l-one (6) in 66% yield from 3 (Scheme 2). The ketone 6 upon treatment with hydroxylamine hydrochloride and pyridine in absolute ethanol furnished as anticipated exclusively the E-isomer of the oxime derivative 7 (83%), i. e. the isomer corresponding to that hydroxy hydroxylamine precursor which is sterically less crowded.…”

mentioning

confidence: 99%

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A New Synthetic Route to (±)‐Perhydrohistrionicotoxin

Corey

Petrzilka

Ueda

1977

Helvetica Chimica Acta

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Starting from ethyl 2‐cyclohexen‐1‐carboxylate (3) the total synthesis of the perhydrohistrionicotoxin intermediate 23 was achieved in 25% overall‐yield. The two key steps involve a positionally specific addition of HOBr to the oxime‐olefin 7 and the alkylation of bromooxime 17 with 1‐lithio‐1‐butyne. The latter represents a novel method for stereospecific and position‐specific introduction of a nucleophilic butyl equivalent in α‐position to a ketonic carbonyl group.

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“…film): 3020, , 1028 (7). To a solution of 6.24 g (41.6 mmol) of the spiro [4,5]dec-6en-I-one (6) and 16.9 ml ( 5 mol-equiv.) of pyridine in 12 ml of abs.…”

Section: Aikylation Of Ethyl 2-cyclohexen-l-carboxylate (3)mentioning

confidence: 99%

Section: Aikylation Of Ethyl 2-cyclohexen-l-carboxylate (3)mentioning

confidence: 99%

Section: Aikylation Of Ethyl 2-cyclohexen-l-carboxylate (3)mentioning

confidence: 99%

Section: Spiro[45]dec-6-en-z-one Oximementioning

confidence: 99%

mentioning

confidence: 99%

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A New Synthetic Route to (±)‐Perhydrohistrionicotoxin

Corey

Petrzilka

Ueda

1977

Helvetica Chimica Acta

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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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Mechanochemical Birch Reduction with Low Reactive Alkaline Earth Metals

Nallaparaju,

Satsi,

Merzhyievskyi

et al. 2024

Angewandte Chemie

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Birch reduction and similar dissolved metal‐type transformations hold significant importance in the organic synthesis toolbox. Historically, the field has been dominated by alkali metal reductants. In this study, we report that largely neglected, low‐reactive alkaline earth metals can become powerful and affordable reductants when used in a ball mill under essentially solvent‐free conditions, in the presence of ethylenediamine and THF as liquid additives. Calcium can reduce both electron‐deficient and electron‐rich arenes, with yields of products similar to those obtained with lithium metal. Magnesium reveals enhanced reducing power, enabling the reduction of benzoic acids while keeping electron‐rich aromatic moieties intact and allows for chemoselective transformations. The developed mechanochemical approach uses readily available and safer‐to‐handle metals, operates under air and ambient temperature conditions, and can be used for gram‐scale preparations. Finally, we demonstrate that the developed conditions can be used for other dissolved metal‐type reductive transformations, including reductive amination, deoxygenation, dehalogenation, alkene and alkyne reductions.

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Reduction of benzene nucleus with magnesium and alcohol in liquid ammonia

Cited by 12 publications

References 1 publication

A New Synthetic Route to (±)‐Perhydrohistrionicotoxin

A New Synthetic Route to (±)‐Perhydrohistrionicotoxin

TheBirch Reduction of Aromatic Compounds

Mechanochemical Birch Reduction with Low Reactive Alkaline Earth Metals

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