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Silylaryl Halides Can Replace Triflates as Aryne Precursors
Milad Mesgar1, Olafs Daugulis1
1Department of Chemistry, University of Houston , Houston, Texas 77204-5003, United States.
Organic Letters
|July 15, 2016
Summary
New silylaryl halides offer a streamlined, one-step synthesis for generating arynes. These precursors enable efficient ortho-arylation of anilines and addition reactions with amides and ureas, simplifying complex organic synthesis.
Area of Science:
- Organic Chemistry
- Synthetic Methodology
Background:
- Arynes are highly reactive intermediates crucial for organic synthesis.
- Generating arynes typically requires specific precursors like silylaryl triflates.
- A need exists for more accessible and efficient aryne precursors.
Purpose of the Study:
- To develop a facile one-step method for preparing silylaryl halides.
- To demonstrate the utility of these new precursors for aryne generation.
- To showcase novel synthetic transformations utilizing these aryne precursors.
Main Methods:
- One-step synthesis of silylaryl bromides and iodides from commercial materials.
- Generation of arynes under mild conditions similar to silylaryl triflates.
- Application in three distinct organic transformations: ortho-arylation, aryne addition to amides, and reaction with ureas.
Main Results:
- Silylaryl bromides and iodides were successfully synthesized in a single step.
- These precursors efficiently generated arynes under established conditions.
- Successful application in ortho-arylation of N-tritylanilines, intermolecular addition to amides, and reaction with ureas.
- Demonstrated advantage of one-step preparation over silylaryl triflates.
Conclusions:
- Silylaryl halides represent a practical and efficient alternative to silylaryl triflates for aryne generation.
- The one-step synthesis and broad applicability expand synthetic possibilities in organic chemistry.
- This method simplifies access to valuable aryne intermediates for further functionalization.
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