Iron(I)-induced demethanation of tert-butyl-substituted nitriles in the gas phase. A case of remote functionalization of carbon-carbon bonds

Tilmann Prüsse, Carlito B Lebrilla, Thomas Drewello, Helmut Schwarz

Research output: Contribution to journalArticle

34 Scopus citations

Abstract

Experiments are described that indicate that the Fe+-induced reductive demethanation of 8,8-dimethylnonanenitrile (11) follows a 1,2-elimination mode in which 90% of the CH4 is generated from the tert-butyl group. The actual reaction sequence seems to commence with oxidative addition of a remote C-C bond to the complexed transition-metal ion, followed by a β-hydrogen migration. There is no experimental evidence for the operation of the long-sought-after β-methyl migration in the system studied. Other processes examined include the collision-induced losses of H2, H2/CH4, CH4/CH4, C4H8, and H2/C4H8 versus C4H10, C5H12, and C6H12, respectively, from the RCN/Fe+ complex. Deuterium-labeling experiments are mandatory for an understanding of the reaction pathways.

Original languageEnglish (US)
Pages (from-to)5986-5993
Number of pages8
JournalJournal of the American Chemical Society
Volume110
Issue number18
StatePublished - 1988
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)

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