Reduction of Tertiary Phosphine Oxides with DIBAL-H

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Abstract

The reduction of tertiary phosphine oxides (TPOs) and sulfides with diisobutylaluminum hydride (DIBAL-H) has been studied in detail. An extensive solvent screen has revealed that hindered aliphatic ethers, such as MTBE, are optimum for this reaction at ambient temperature. Many TPOs undergo considerable reduction at ambient temperature and then stall due to inhibition. ³¹P and ¹³C NMR studies using isotopically labeled substrates as well as competition studies have revealed that the source of this inhibition is tetraisobutyldialuminoxane (TIBAO), which builds up as the reaction proceeds. TIBAO selectively coordinates the TPO starting material, preventing further reduction. Several strategies have been found to circumvent this inhibition and obtain full conversion with this extremely inexpensive reducing agent for the first time. Practical reduction protocols for these critical targets have been developed.

Citing Articles

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This article has been cited by 4 ACS Journal articles (4 most recent appear below).

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  Toxicological Assessment of 2-Methyltetrahydrofuran and Cyclopentyl Methyl Ether in Support of Their Use in Pharmaceutical Chemical Process Development

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  • Toxicological Assessment of 2-Methyltetrahydrofuran and Cyclopentyl Methyl Ether in Support of Their Use in Pharmaceutical Chemical Process Development

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    Organic Process Research & Development2011 15 (4), 939-941

    Herein we document our evaluation of the oral toxicity of MeTHF and CPME as determined in three month repeat-dose toxicity studies in rats as well as a battery of tests conducted under Good Laboratory Practice (GLP) to assess induction of micronuclei, ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Single-Step Synthesis of Secondary Phosphine Oxides

  Aaron J. Bloomfield, Jack M. Qian, and Seth B. Herzon
  Organometallics2010 29 (18), 4193-4195

  • Single-Step Synthesis of Secondary Phosphine Oxides

    Aaron J. Bloomfield, Jack M. Qian, and Seth B. Herzon
    Organometallics2010 29 (18), 4193-4195

    We report that in the presence of trifluoroacetic acid primary phosphines undergo efficient addition to aldehydes to form the corresponding secondary phosphine oxides in 47−97% yield. This transformation is compatible with aryl and alkyl phosphines, as ...

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• 

  Phosphine-Catalyzed Reductions of Alkyl Silyl Peroxides by Titanium Hydride Reducing Agents: Development of the Method and Mechanistic Investigations

  Jason R. Harris, M. Taylor Haynes, II, Andrew M. Thomas and K. A. Woerpel
  The Journal of Organic Chemistry2010 75 (15), 5083-5091

  • Phosphine-Catalyzed Reductions of Alkyl Silyl Peroxides by Titanium Hydride Reducing Agents: Development of the Method and Mechanistic Investigations

    Jason R. Harris, M. Taylor Haynes, II, Andrew M. Thomas and K. A. Woerpel
    The Journal of Organic Chemistry2010 75 (15), 5083-5091

    A method that allows for the reduction of protected hydroperoxides by employing catalytic amounts of phosphine is presented. The combination of a titanium(IV) alkoxide and a siloxane allowed for the chemoselective reduction of phosphine oxides in the ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Mechanistic Insight into the Reduction of Tertiary Phosphine Oxides by Ti(OiPr)₄/TMDS

  Christelle Petit, Alain Favre-Reguillon, Bélen Albela, Laurent Bonneviot, Gerard Mignani and Marc Lemaire
  Organometallics2009 28 (22), 6379-6382

  • Mechanistic Insight into the Reduction of Tertiary Phosphine Oxides by Ti(OiPr)₄/TMDS

    Christelle Petit, Alain Favre-Reguillon, Bélen Albela, Laurent Bonneviot, Gerard Mignani and Marc Lemaire
    Organometallics2009 28 (22), 6379-6382

    The reduction mechanism of tertiary phosphine oxides by Ti(OiPr)4/hydrosiloxane was studied. Strong improvement was achieved using a drying agent. ESR spectra of the reaction mixture give evidence for a single electronic transfer (SET) mechanism.

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