The reaction of n-butyllithium and potassium t-amyloxide with butenes

Trepka, William J.; Favre, J.A.; Sonnenfeld, R. J.

doi:10.1016/s0022-328x(00)82063-x

Cited by 16 publications

(1 citation statement)

References 15 publications

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“…Therein the contribution AEq of quadrupole excitations to the correlation energy is given by AEq = (1 -CqWsd (7) Iai22ai23ai2lb224ai25ai22b226ai2lb]23b22…”

Section: Theoretical Approachmentioning

confidence: 99%

1,1-Dilithioethylene. A ground-state triplet olefin with nearly free rotation about the double bond

Laidig¹,

Schaefer²

1979

J. Am. Chem. Soc.

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“…Therein the contribution AEq of quadrupole excitations to the correlation energy is given by AEq = (1 -CqWsd (7) Iai22ai23ai2lb224ai25ai22b226ai2lb]23b22…”

Section: Theoretical Approachmentioning

confidence: 99%

1,1-Dilithioethylene. A ground-state triplet olefin with nearly free rotation about the double bond

Laidig¹,

Schaefer²

1979

J. Am. Chem. Soc.

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A Tandem Hexaannulation Reaction of Benzyllithium Involving Base-Induced Cyclodehydrogenation

et al. 1999

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The Metallation‐Elimination Reaction, II. Monocyclic Anions and Polyanions

et al. 1983

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Equimolar mixtures of n-butyllithium and potassium tert-amyloxide effect metallation and metal hydride elimination of cyclic olefins directly to give conjugated anions and polyanions in a single operation. 1-Methyl-1-cycloalkenes or methylenecycloalkanes are particularly well suited and give highly unsaturated products. Odd-membered rings eliminate better than their even-membered counterparts, and eight-membered rings eliminate particularly slowly. Reactions with methyl iodide and trimethylsilyl chloride proceed smoothly in high yield. Die Metallierungs-Eliminierungs-Reaktion, I1 l) Monocyclische Anionen und PolyanionenAquimolare Mischungen von n-Butyllithium und Kalium-tert-amyloxid bewirken Metallierung und Metallhydrid-Eliminierung an cyclischen Olefinen und fiihren direkt in einer Eintopf-Reaktion zu konjugierten Anionen und Polyanionen. 1-Methyl-1-cycloalkene oder Methylencycloalkane sind besonders gut geeignet und geben stark ungesattigte Produkte. Ringe mit ungerader Kohlenstoffzahl eliminieren besser als die geradzahligen. Achtgliedrige Ringe eliminieren extrem langsam. Reaktionen mit Methyliodid und Trimethylsilylchlorid verlaufen glatt und in guter Ausbeute.Mixtures of n-butyllithium (BuLi) with potassium tertiary alkoxides are highly active metallation reagents. Lochmann's base (BuLi/KOtBu) a) has been used extensively to generate anions and dianions2-'), but other potassium tertiary alkoxides such as potassium menthoxide') or potassium tert-amyloxide") have the advantage .of solubility in hydrocarbon solvents. In the first paper of this series") a BuLi/potassium tert-amyloxide (BuLi/KOtAm) mixture was shown to be effective for the catalysis of metal hydride eliminations, which normally require higher temperat~res'~-l') or are carried out using hydride acceptor^'^-^^). By combining the metallation and elimination reactions we were able to prepare the heptafulvene dianion") (l), which is unaccessible by direct metallation (BuLi adds to cycloheptatrienes). Bates' calculations 26) indicate 1 to be one of the least stable dianions which have been prepared.Path A involves a dianion intermediate formed directly by deprotonation of a preformed ally1 anion. Path B is more conventional and involves a neutral diene inter- Chem. Ber. 126(1983) The Metallation-Elimination Reaction, I1

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The reaction of n-butyllithium and potassium t-amyloxide with butenes

Cited by 16 publications

References 15 publications

1,1-Dilithioethylene. A ground-state triplet olefin with nearly free rotation about the double bond

1,1-Dilithioethylene. A ground-state triplet olefin with nearly free rotation about the double bond

A Tandem Hexaannulation Reaction of Benzyllithium Involving Base-Induced Cyclodehydrogenation

The Metallation‐Elimination Reaction, II. Monocyclic Anions and Polyanions

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