A useful methoxyvinyl cation equivalent: α-t-butyldimethylsilyl-α-methoxyacetaldehyde

Christopher D. Mccune, Matthew L. Beio, Jacob A. Friest, Sandeep Ginotra, David B. Berkowitz

Research output: Contribution to journalArticlepeer-review

3 Scopus citations


Abstract Described are the synthesis and application of α-t-butyldimethylsilyl-α-methoxyacetaldehyde as a formal methoxyvinyl cation equivalent. Addition of Grignard reagents to the title aldehyde, followed by treatment of the intermediate β-hydroxysilanes with KH, gives good yields of largely Z-methoxyvinylated products. Assuming a Peterson-like elimination mechanism, one can infer that the Grignard addition proceeds with high syn selectivity. These results are consistent with a chelation control model involving coordination to the α-methoxy group in the title aldehyde rather than an alternative stereoelectronic Felkin-Anh-type model. It must be noted that a steric Felkin-Anh model also accounts for the observed stereochemistry. All told, the title reagent can be employed to efficiently append a Z-configured methoxyvinyl group to an appropriate R-M species, in two steps.

Original languageEnglish (US)
Article number45992
Pages (from-to)3575-3579
Number of pages5
JournalTetrahedron Letters
Issue number23
StatePublished - May 25 2015


  • Chelation control
  • Methoxyvinylation
  • Peterson elimination
  • Rieke magnesium
  • Steric Felkin-Anh model
  • α-Silyl-α-methoxyacetaldehyde

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry


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