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Type II Anion Relay Chemistry: Conformational Constraints To Achieve Effective [1,5]-Vinyl Brook Rearrangements.

Qi Liu1, Yu Chen2, Xiao Zhang2

  • 1Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104, United States.

Journal of the American Chemical Society
|June 15, 2017
PubMed
Summary
This summary is machine-generated.

Researchers developed bifunctional linchpins for efficient [1,5]-Brook rearrangements. These linchpins enable alkylations and cross-coupling reactions of stabilized carbanions, advancing synthetic organic chemistry.

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Area of Science:

  • Organic Chemistry
  • Synthetic Methodology
  • Organometallic Chemistry

Background:

  • Brook rearrangements are crucial for carbon-silicon bond formation.
  • Vinyl silanes offer unique reactivity pathways in rearrangements.
  • Conformational control is key to directing reaction selectivity.

Purpose of the Study:

  • To design and synthesize novel bifunctional linchpins.
  • To achieve efficient [1,5]-Brook rearrangements using vinyl silanes.
  • To apply these linchpins in anion relay chemistry (ARC) for further functionalization.

Main Methods:

  • Synthesis of conformationally anchored linchpins.
  • Investigation of [1,5]-Brook rearrangements with vinyl silanes.
  • Application in type II anion relay chemistry (ARC).
  • Palladium-catalyzed cross-coupling reactions (CCR).
  • Density Functional Theory (DFT) calculations.

Main Results:

  • Successful design and synthesis of bifunctional linchpins.
  • Efficient [1,5]-Brook rearrangements were achieved.
  • Alkylation and Pd-mediated CCR of sp2-stabilized carbanions were enabled via ARC.
  • DFT calculations elucidated reaction mechanisms and trends.

Conclusions:

  • Conformationally restrained linchpins facilitate efficient [1,5]-Brook rearrangements.
  • Type II ARC provides a versatile platform for carbanion functionalization.
  • Understanding of vinyl Brook rearrangement mechanisms and influencing factors was gained.