Catalytic activation and functionalization of C-H bonds. Aldimine formation by the insertion of isonitriles into aromatic C-H bonds

Journal Article · Wed Aug 05 04:00:00 EDT 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00250a060· OSTI ID:6086153

Jones, W D; Foster, G P; Putinas, J M

Many examples of the activation of aromatic and aliphatic carbon-hydrogen bonds by homogeneous transition-metal complexes have appeared over the past few years, offering attractive new routes to organometallic species. While several of these reports involve oxidative addition of low valent metal complexes to alkanes or arenes, these new adducts have not proven to be useful for the generation of functionalized hydrocarbon products. Reports of successful metal-based alkane functionalization include free radical oxidations, intramolecular cyclizations of alkyl carbenoid species to given cyclopentanones, aromatic isonitrile insertion to give indoles, and alkane dehydrogenation to produce olefins. Arene functionalization reactions commonly depend upon the presence of tethering groups, although the production of benzaldehyde, benzoic acid, styrene, and phenylsiloxane insertion products have been recently reported. They report here a new type of iron catalyzed insertion of isonitrile into the C-H bond of arenes to produce aldimines (eq 1). RNC + C/sub 6/H/sub 6/ (Fe) ..-->.. ..delta..G/sup 0/ approx. = -11 Kcal/mol C/sub 6/H/sub 5/ - CH = NR (1).

• Research Organization: Univ. of Rochester, NY
• DOE Contract Number: FG02-86ER13569
• OSTI ID: 6086153
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:16; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
AROMATICS
CARBON
CARBONIC ACID DERIVATIVES
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL BONDS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
DATA
ELEMENTS
EXPERIMENTAL DATA
HYDROGEN
IMINES
INFORMATION
IRON
ISONITRILES
METALS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
SYNTHESIS
TRANSITION ELEMENTS