Synthesis of 2-Pyrrolidinones by Palladium-Catalyzed [3+2] Cycloaddition of Isocyanates

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Pd/DPEphos catalyzes the [3+2] cycloaddition of various alkyl isocyanates with 2-acetoxymethyl-3-allyltrimethylsilane as a synthetic equivalent of trimethylenemethane (TMM). Taking advantage of 2-acetoxymethyl-3-allyltrimethylsilane acting both as nucleophile as well as electrophile this reaction gives a convenient access to 5-ring lactams with an exocyclic alkene moiety. The formation of the β,γ-unsaturated 2-pyrrolidinones occurs without olefin isomerization and without epimerization of the stereogenic centers. Mechanistic investigations suggest an initial N-allylation of the isocyanate followed by nucleophilic ring closure furnishing the desired 2-pyrrolidinones.
LanguageEnglish
Pages581-585
Number of pages5
JournalSynlett
Volume30
Issue number05
DOIs
StatusPublished - 2019

Fingerprint

Isocyanates
Cycloaddition
Palladium
Alkenes
Allylation
Lactams
Nucleophiles
Isomerization
allyltrimethylsilane
2-pyrrolidone
trimethylenemethane

Keywords

  • allyl silanes
  • cycloaddition
  • heterocycles
  • isocyanates
  • lactams
  • palladium
  • Tsuji-Trost allylation

Fields of Expertise

  • Human- & Biotechnology

Cite this

Synthesis of 2-Pyrrolidinones by Palladium-Catalyzed [3+2] Cycloaddition of Isocyanates. / Kljajic, Marko; Schlatzer, Thomas; Breinbauer, Rolf.

In: Synlett, Vol. 30, No. 05, 2019, p. 581-585.

Research output: Contribution to journalArticleResearchpeer-review

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abstract = "Pd/DPEphos catalyzes the [3+2] cycloaddition of various alkyl isocyanates with 2-acetoxymethyl-3-allyltrimethylsilane as a synthetic equivalent of trimethylenemethane (TMM). Taking advantage of 2-acetoxymethyl-3-allyltrimethylsilane acting both as nucleophile as well as electrophile this reaction gives a convenient access to 5-ring lactams with an exocyclic alkene moiety. The formation of the β,γ-unsaturated 2-pyrrolidinones occurs without olefin isomerization and without epimerization of the stereogenic centers. Mechanistic investigations suggest an initial N-allylation of the isocyanate followed by nucleophilic ring closure furnishing the desired 2-pyrrolidinones.",
keywords = "allyl silanes, cycloaddition, heterocycles, isocyanates, lactams, palladium, Tsuji-Trost allylation",
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AU - Breinbauer,Rolf

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N2 - Pd/DPEphos catalyzes the [3+2] cycloaddition of various alkyl isocyanates with 2-acetoxymethyl-3-allyltrimethylsilane as a synthetic equivalent of trimethylenemethane (TMM). Taking advantage of 2-acetoxymethyl-3-allyltrimethylsilane acting both as nucleophile as well as electrophile this reaction gives a convenient access to 5-ring lactams with an exocyclic alkene moiety. The formation of the β,γ-unsaturated 2-pyrrolidinones occurs without olefin isomerization and without epimerization of the stereogenic centers. Mechanistic investigations suggest an initial N-allylation of the isocyanate followed by nucleophilic ring closure furnishing the desired 2-pyrrolidinones.

AB - Pd/DPEphos catalyzes the [3+2] cycloaddition of various alkyl isocyanates with 2-acetoxymethyl-3-allyltrimethylsilane as a synthetic equivalent of trimethylenemethane (TMM). Taking advantage of 2-acetoxymethyl-3-allyltrimethylsilane acting both as nucleophile as well as electrophile this reaction gives a convenient access to 5-ring lactams with an exocyclic alkene moiety. The formation of the β,γ-unsaturated 2-pyrrolidinones occurs without olefin isomerization and without epimerization of the stereogenic centers. Mechanistic investigations suggest an initial N-allylation of the isocyanate followed by nucleophilic ring closure furnishing the desired 2-pyrrolidinones.

KW - allyl silanes

KW - cycloaddition

KW - heterocycles

KW - isocyanates

KW - lactams

KW - palladium

KW - Tsuji-Trost allylation

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