Silicon as a powerful control element in HDDA chemistry: redirection of innate cyclization preferences, functionalizable tethers, and formal bimolecular HDDA reactions

Mandy Lynn, Merrick Pierson Smela, Thomas R. Hoye

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)13902-13908
Number of pages7
JournalChemical Science
Volume12
Issue number41
DOIs
StatePublished - Nov 7 2021

Bibliographical note

Funding Information:
The National Institute of General Medical Sciences of the U.S. Department of Health and Human Services (R35 GM127097) provided support for this research. A portion of the NMR spectral data was obtained using an instrument funded through the NIH shared Instrumentation Grant program (S10OD011952). Mass spectral data were collected at the Masonic Cancer Center, University of Minnesota in the Analytical Biochemistry Shared Resource laboratory; instrumentation there was partially funded by a Cancer Center Support Grant (CA-77598). M. P. S. was supported in part by a Heisig-Gleysteen Fellowship. Computational studies were performed using resources provided by the University of Minnesota Supercomputing Institute (MSI).

Publisher Copyright:
© The Royal Society of Chemistry 2021.

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