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 journalArticle

2 Citations (Scopus)

Abstract

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
Volume56
Issue number23
DOIs
StatePublished - May 25 2015

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Aldehydes
Cations
Stereochemistry
Chelation
2-methoxyacetaldehyde

Keywords

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

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

Cite this

A useful methoxyvinyl cation equivalent : α-t-butyldimethylsilyl-α-methoxyacetaldehyde. / Mccune, Christopher D.; Beio, Matthew L.; Friest, Jacob A.; Ginotra, Sandeep; Berkowitz, David B.

In: Tetrahedron Letters, Vol. 56, No. 23, 45992, 25.05.2015, p. 3575-3579.

Research output: Contribution to journalArticle

Mccune, Christopher D. ; Beio, Matthew L. ; Friest, Jacob A. ; Ginotra, Sandeep ; Berkowitz, David B. / A useful methoxyvinyl cation equivalent : α-t-butyldimethylsilyl-α-methoxyacetaldehyde. In: Tetrahedron Letters. 2015 ; Vol. 56, No. 23. pp. 3575-3579.
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AU - Beio, Matthew L.

AU - Friest, Jacob A.

AU - Ginotra, Sandeep

AU - Berkowitz, David B

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N2 - 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.

AB - 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.

KW - Chelation control

KW - Methoxyvinylation

KW - Peterson elimination

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KW - Steric Felkin-Anh model

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