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Updated: Oct 13, 2025

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
Silicon as a powerful control element in HDDA chemistry: redirection of innate cyclization preferences,
Mandy Lynn1, Merrick Pierson Smela1, Thomas R Hoye1
1Department of Chemistry, University of Minnesota 207 Pleasant St. SE Minneapolis MN 55455 USA hoye@umn.edu.
Abstract:
The 1,3-diyne and diynophile in hexadehydro-Diels-Alder (HDDA) reaction substrates are typically tethered by linker units that consist of C, O, N, and/or S atoms. We describe here a new class of polyynes based on silicon-containing tethers that can be disposed of and/or functionalized subsequent to the HDDA reaction. The cyclizations are efficient, and the resulting benzoxasiloles are amenable to protodesilylation, halogenation, oxygenation, and arylation reactions. The presence of the silicon atom can also override the innate mode of cyclization in some cases, an outcome attributable to a β-silyl effect on the structure of intermediate diradicals. Overall, this strategy equates formally to an otherwise unknown, bimolecular HDDA reaction and expands the versatility of this body of aryne chemistry.
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