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gamma-hydroxy unsaturated nitriles: chelation-controlled conjugate additions.

F F Fleming1, Q Wang, O W Steward

  • 1Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282-1530, USA. fleming@duq.edu

Organic Letters
|May 18, 2000
PubMed
Summary

Chelation using Grignard reagents enables difficult anionic conjugate additions with gamma-hydroxy unsaturated nitriles. This novel reaction pathway efficiently creates diverse chemical structures through addition-alkylation.

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Area of Science:

  • Organic Chemistry
  • Organometallic Chemistry

Background:

  • Anionic conjugate addition reactions are crucial in organic synthesis.
  • Chelation control can enhance reactivity and selectivity in organic transformations.

Purpose of the Study:

  • To develop a novel method for promoting difficult anionic conjugate addition reactions.
  • To explore the use of Grignard reagents and chelation in facilitating these transformations.

Main Methods:

  • Deprotonation of gamma-hydroxy unsaturated nitriles using tert-butylmagnesium chloride (t-BuMgCl).
  • Addition of a second Grignard reagent to form an intermediate chelate.
  • Intramolecular conjugate addition triggered by the chelate.
  • Stereoselective alkylation of the intermediate anion with benzyl bromide (BnBr).

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Main Results:

  • Chelation between gamma-hydroxy unsaturated nitriles and Grignard reagents effectively promotes anionic conjugate addition.
  • Structurally diverse Grignard reagents were added with high efficiency.
  • The reaction proceeds via an intermediate chelate and intramolecular conjugate addition.
  • The intermediate anion was stereoselectively alkylated, yielding the final product.

Conclusions:

  • This study presents an efficient chelation-controlled method for anionic conjugate addition using Grignard reagents.
  • The developed addition-alkylation reaction offers a versatile route to diverse chemical structures.
  • The methodology demonstrates broad applicability with various Grignard reagents.