Cyclobutanone as an electrophile for lithiated phosphine oxides: ‘Internal quench’ conditions

Guéguen, Catherine; O’Brien, Peter; Warren, Stuart; Wyatt, Paul

doi:10.1016/s0022-328x(96)06691-0

Cited by 15 publications

(2 citation statements)

References 21 publications

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“…Initially, we lithiated mixtures of two of the three phosphine derivatives with LDA in the presence of cyclobutanone as an internal trapping agent (Scheme 9). 14 Cyclobutanones enolise very slowly and we envisaged employing this method to study the relative rates of lithiation via the relative ratio of the addition products. By keeping the level of LDA sufficiently low, the reaction kinetics could be approximated to pseudo-first-order in base.…”

Section: Lithiated Phosphine Sulfides Have Been Employed In Reactionsmentioning

confidence: 99%

The lithiation and acyl transfer reactions of phosphine oxides, sulfides and boranes in the synthesis of cyclopropanes

et al. 2009

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Phosphine oxides are lithiated much faster than phosphine sulfides and phosphine boranes. Phosphine sulfides are in turn lithiated much more readily than phosphine boranes. It was possible to trap a phosphine sulfide THF in one case which upon treatment with t-BuOK gave cyclopropane, showing that phosphine sulfides readily undergo both phosphinoyl transfer and cyclopropane ring closure just like their phosphine oxide counterparts. The obtained data show that phosphine oxides are easily lithiated and undergo phosphoryl transfer much more readily and faster than phosphine sulfides and phosphine boranes. The observations suggest that it would be possible to perform reactions involving phosphine oxides in the presence of phosphine boranes or phosphine sulfides, potentially allowing regioselective alkylation of phosphine oxides in the presence of phosphine boranes or phosphine sulfides.

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Section: Lithiated Phosphine Sulfides Have Been Employed In Reactionsmentioning

confidence: 99%

The lithiation and acyl transfer reactions of phosphine oxides, sulfides and boranes in the synthesis of cyclopropanes

et al. 2009

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“…(Scheme 1), we found that the use of other internal electrophiles resulted in Baylis-Hillman like products. Reaction of 1 (Ar = Ph) with methyl iodide gave a 76% yield of the phosphine oxide 4 and reaction with cyclobutanone, which we have used previously as an internal quench, 11 gave a 50% yield of the hydroxyphosphine oxide 5.…”

Section: Resultsmentioning

confidence: 84%

Allene synthesis by an asymmetric Baylis–Hillman style reaction on vinylphosphine oxides

Fox

Medlock

Vosser

et al. 2001

J. Chem. Soc., Perkin Trans. 1

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A novel reaction has been discovered with a mechanism similar to the Baylis-Hillman reaction. Reaction of a vinylic phosphine oxide with (R)-N-lithio-α-methylbenzylbenzylamine 2 in the presence of an aldehyde gave hydroxyphosphine oxides in good to moderate yields and moderate to poor enantioselectivities. The hydroxyphosphine oxides undergo the Horner-Wittig elimination reaction to produce allenes. Baylis-Hillman reactions of vinylic phosphine oxides with tertiary amines were also investigated.

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Rings containing Phosphorus

Шестопалов

Shestopalov

2008

Comprehensive Heterocyclic Chemistry III

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Cyclobutanone as an electrophile for lithiated phosphine oxides: ‘Internal quench’ conditions

Cited by 15 publications

References 21 publications

The lithiation and acyl transfer reactions of phosphine oxides, sulfides and boranes in the synthesis of cyclopropanes

The lithiation and acyl transfer reactions of phosphine oxides, sulfides and boranes in the synthesis of cyclopropanes

Allene synthesis by an asymmetric Baylis–Hillman style reaction on vinylphosphine oxides

Rings containing Phosphorus

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