Silver-catalyzed silacyclopropenation of 1-heteroatom-substituted alkynes and subsequent rearrangement reactions

Timothy B. Clark, Keith Woerpel

Research output: Contribution to journalArticle

Abstract

Silver phosphate-catalyzed silylene transfer from silacyclopropane 1 to 1-heteroatom-substituted alkynes resulted in alkoxy-, amino-, and alkylthiolate-substituted silacyclopropenes. Silver-catalyzed silylene transfer to 1-halo- and 1-sulfonyl-substituted alkynes led to insertion of silylene into the carbon-heteroatom bond. Attempts at copper-catalyzed insertion of carbonyl compounds into heteroatom-substituted silacyclopropenes led to rearrangement into silicon-substituted alkynes with a net silylene insertion into the carbon-heteroatom bond. Mechanistic studies were conducted utilizing crossover experiments. A mechanism involving transmetalation/elimination was supported by the observation of crossovers in double-labeling experiments for alkynyl sulfides, halides, and sulfones.

Original languageEnglish (US)
Pages (from-to)6212-6219
Number of pages8
JournalOrganometallics
Volume24
Issue number25
DOIs
StatePublished - Dec 5 2005

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Alkynes
alkynes
Silver
insertion
silver
crossovers
Carbon
Carbonyl compounds
Sulfones
carbonyl compounds
sulfones
carbon
Sulfides
Silicon
Labeling
marking
halides
sulfides
Copper
elimination

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Silver-catalyzed silacyclopropenation of 1-heteroatom-substituted alkynes and subsequent rearrangement reactions. / Clark, Timothy B.; Woerpel, Keith.

In: Organometallics, Vol. 24, No. 25, 05.12.2005, p. 6212-6219.

Research output: Contribution to journalArticle

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