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Abstract

The preparation of styrenes by palladium-catalyzed cross-coupling of aromatic iodides and bromides with divinyltetramethyldisiloxane (DVDS) in the presence of inexpensive silanolate activators has been developed. To facilitate the discovery of optimal reaction conditions, Design of Experiment (DoE) protocols were used. By the guided selection of reagents, stoichiometries, temperatures, and solvents, the vinylation reaction was rapidly optimized with three stages consisting of ca. 175 experiments (of a possible 1440 combinations). A variety of aromatic iodides undergo cross-coupling at room temperature in the presence of potassium trimethylsilanoate using Pd(dba)₂ in DMF in good yields. Triphenylphosphine oxide is needed to extend catalyst lifetime. Application of these conditions to aryl bromides was accomplished by the development of two complementary protocols. First, the direct implementation of the successful reaction conditions using aryl iodides at elevated temperature in THF provided the corresponding styrenes in good to excellent yields. Alternatively, the use of potassium triethylsilanolate and a bulky “Buchwald-type” ligand allows for the vinylation reactions to occur at or just above room temperature. A wide range of bromides underwent coupling in good yields for each of the protocols described.

Citing Articles

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This article has been cited by 11 ACS Journal articles (5 most recent appear below).

• 

  Palladium-Catalyzed Hiyama Cross-Coupling of Aryltrifluorosilanes with Aryl and Heteroaryl Chlorides

  Gary A. Molander and Laura Iannazzo
  The Journal of Organic Chemistry2011 76 (21), 9182-9187

  • Palladium-Catalyzed Hiyama Cross-Coupling of Aryltrifluorosilanes with Aryl and Heteroaryl Chlorides

    Gary A. Molander and Laura Iannazzo
    The Journal of Organic Chemistry2011 76 (21), 9182-9187

    An efficient, palladium-catalyzed Hiyama cross-coupling reaction of aryltrifluorosilanes with aryl chlorides has been developed. A wide variety of functionalized biaryl derivatives were isolated in good to excellent yields. The scope of this reaction has ...

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

  One-Step Preparation of Functionalized (E)-Vinylsilanes from Aldehydes

  Diane S. W. Lim and Edward A. Anderson
  Organic Letters2011 Article ASAP

  • One-Step Preparation of Functionalized (E)-Vinylsilanes from Aldehydes

    Diane S. W. Lim and Edward A. Anderson
    Organic Letters2011 Article ASAP

    Functionalized (E)-vinylsilanes have been prepared in one step from a wide range of aldehydes, via a chromium(II)-mediated olefination with novel dihalomethylsilane reagents, in moderate to excellent yields and with excellent stereoselectivity.

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

  Diversity-Oriented Synthesis of Disubstituted Alkenes Using Masked Silanols

  Hannah F. Sore, David T. Blackwell, Simon J. F. MacDonald and David R. Spring
  Organic Letters2010 12 (12), 2806-2809

  • Diversity-Oriented Synthesis of Disubstituted Alkenes Using Masked Silanols

    Hannah F. Sore, David T. Blackwell, Simon J. F. MacDonald and David R. Spring
    Organic Letters2010 12 (12), 2806-2809

    The regio- and stereoselective synthesis and subsequent Hiyama cross coupling of pentafluorophenyldimethylvinylsilanes has been developed, thus providing a convenient and robust method for the diversity-oriented synthesis of (E)-, (Z)- and α-...

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

  Ionic Chemistry of Tetravinylsilane Cation (TVS⁺) Formed by Electron Impact: Theory and Experiment

  V. Brites, G. Chambaud and M. Hochlaf, J. Kočišek, J. L. Cayao Diaz and Š. Matejčík, F. Krčma
  The Journal of Physical Chemistry A2009 113 (23), 6531-6536

  • Ionic Chemistry of Tetravinylsilane Cation (TVS⁺) Formed by Electron Impact: Theory and Experiment

    V. Brites, G. Chambaud and M. Hochlaf, J. Kočišek, J. L. Cayao Diaz and Š. Matejčík, F. Krčma
    The Journal of Physical Chemistry A2009 113 (23), 6531-6536

    We performed experimental and ab initio studies on tetravinylsilane cation (TVS+) and its ionic and neutral fragmentation products. The aim of the study is the assignment of the products formed in electron impact ionization reaction of TVS. The ...

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

  The Interplay of Invention, Discovery, Development, and Application in Organic Synthetic Methodology: A Case Study

  Scott E. Denmark
  The Journal of Organic Chemistry2009 74 (8), 2915-2927

  • The Interplay of Invention, Discovery, Development, and Application in Organic Synthetic Methodology: A Case Study

    Scott E. Denmark
    The Journal of Organic Chemistry2009 74 (8), 2915-2927

    This Perspective chronicles the conceptual development, proof of principle, exploration of scope, mechanistic investigations, and applications in natural product total synthesis of palladium-catalyzed cross-coupling reactions of silicon derivatives. The ...

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

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