Catalytic hydrogenolysis of cyclopropanes: metal insertion into a saturated carbon-carbon bond as the key step

Hydrogenolytic ring cleavage of gem-difluorocyclopropanes, e.g. I and II, occurs exclusively at the carbon-carbon bond opposite to the halogen-bearing center and affords mainly gem-difluoroalkanes, e.g. MeCH2CF2(CH2)3Me and III, resp. The intermediacy of catalyst/cyclopropane derived adducts (e.g., palladacyclobutanes or 1,3-dipalladiopropanes) is postulated in order to rationalize the formation of monofluorinated and halogen-free byproducts and, in addn., to explain specific substituent effects on the reaction rates. [on SciFinder (R)]


Published in:
Tetrahedron, 47, 7, 1231-8
Year:
1991
Keywords:
Note:
CAN 114:228404
24-2
Alicyclic Compounds
Inst. Chim. Org.,Univ. Lausanne,Lausanne,Switz.
Journal
0040-4020
written in English.
823-70-1; 133744-87-3; 133744-88-4; 133744-89-5; 133744-90-8 Role: RCT (Reactant), RACT (Reactant or reagent) (catalytic hydrogenolysis of); 111-84-2P (Nonane) Role: FORM (Formation, nonpreparative), PREP (Preparation) (formation of, from hydrogenolysis of butenylethyldifluorocyclopropane); 3073-92-5P Role: FORM (Formation, nonpreparative), PREP (Preparation) (formation of, from hydrogenolysis of butoxydifluorocyclopropane); 142-96-1P Role: FORM (Formation, nonpreparative), PREP (Preparation) (formation of, from hydrogenolysis of butoxydifluoromethylcyclopropane); 142-82-5P (Heptane); 133744-93-1P Role: FORM (Formation, nonpreparative), PREP (Preparation) (formation of, from hydrogenolysis of difluoromethylpropylcyclopropane); 291-64-5P (Cycloheptane) Role: FORM (Formation, nonpreparative), PREP (Preparation) (formation of, from hydrogenolysis of difluoronorcarene); 1333-74-0 Role: RCT (Reactant), RACT (Reactant or reagent) (hydrogenolysis, catalytic ,of fluorocyclopropanes); 133895-54-2P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and hydrogenolysis of); 52708-15-3P (4-Fluorononane); 133744-96-4P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of, from hydrogenolysis of butenylethyldifluorocyclopropane); 133744-91-9P; 133744-94-2P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of, from hydrogenolysis of butoxydifluorocyclopropane); 133744-92-0P; 133744-95-3P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of, from hydrogenolysis of butoxydifluoromethylcyclopropane); 33577-38-7P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of, from hydrogenolysis of difluoromethylpropylcyclopropane); 27371-42-2P; 51443-95-9P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of, from hydrogenolysis of difluoronorcarene)
Laboratories:




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