Reactions of Fischer carbene complexes with Electron-deficient olefins: Scope and limitations of this route to donor-acceptor-substituted cyclopropanes

Journal Article · Sat Dec 01 00:00:00 EST 1990 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00162a027· OSTI ID:6109456

Wienand, A; Reissig, H U ^[1]

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1. Inst. fuer Organische Chemie der Technischen Hochschule Darmstadt (West Germany)

The Fischer carbene complex ((CO){sub 5}Cr{double bond}C(OMe)Ph) (1) is able to transfer its carbene ligand to a variety of electron-deficient olefins and provides donor-acceptor-substituted cyclopropanes in good yields. Apt activating groups with respect to the alkene are ester, amide, nitrile, sulfone, and dialkyl phosphonate functions. Methyl vinyl ketone (19) affords products in low yield that may arise from an intermediate cyclopropane derivative. Phenyl vinyl sulfoxide (24) mainly acts as an oxidizing agent, transforming 1 into methyl benzoate. for olefin 24 and {alpha}-(N-methylanilino)acrylonitrile the authors found products that should be formed on an olefin metathesis pathway. The methyl-substituted carbene complex 48 also affords the expected donor-acceptor-substituted cyclopropanes; however, acyclic isomers are formed in higher amounts. The molybdenum and tungsten complexes 55 and 56, respectively, also furnish cyclopropane derivatives, but the yields are lower than with the chromium compound 1. Disubstituted olefins and complex 1 still give the cyclopropanes in moderate yields, while all trisubstituted and most of the difunctionalized alkenes do not react with this Fischer carbene complex. The cyclopropanes synthesized can be deprotonated and alkylated or transformed into ring-opened products. These model reactions demonstrate the synthetic potentials of donor-acceptor-substituted cyclopropanes prepared via Fischer carbene complexes.

• OSTI ID: 6109456
• Journal Information: Organometallics; (United States), Vol. 9:12; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
10 SYNTHETIC FUELS
ALKENES
CHEMICAL REACTIONS
CHROMIUM COMPLEXES
CYCLOALKANES
CHEMICAL PREPARATION
ACRYLONITRILE
ALKYLATION
AMIDES
CARBENES
CARBONYLS
DEUTERATION
ESTERS
FURANS
KETONES
LACTONES
LIGANDS
MOLYBDENUM COMPLEXES
NITRILES
NMR SPECTRA
PHOSPHONATES
REACTION INTERMEDIATES
STEREOCHEMISTRY
SULFONES
TITANIUM CHLORIDES
TUNGSTEN COMPLEXES
ALKANES
CHLORIDES
CHLORINE COMPOUNDS
COMPLEXES
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
ORGANIC SULFUR COMPOUNDS
RADICALS
SPECTRA
SYNTHESIS
TITANIUM COMPOUNDS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties
100200 - Synthetic Fuels- Production- (1990-)