Method for conversion of terminal alkenes to aldehydes using ruthenium (IV) porphyrin catalysts
AssigneeThe University of Hong Kong
InventorsChi-Ming Che, Jian Chen
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Abstract
Aldehydes were obtained in excellent yields from ruthenium-porphyrin-catalyzed oxidation of various terminal alkenes with 2,6-dichloropyridine N-oxide under mild conditions. The aldehydes generated from these ruthenium-catalyzed alkene oxidation reactions can be used in-situ for olefination reactions with ethyl diazoacetate in the presence of PPh3, leading to one-pot diazoacetate olefination starting from alkenes.
Claims19
A method for producing an aldehyde from an unsaturated compound having one or more C═C functional groups, which comprises reacting a pyrldine-N-oxide with the unsaturated compound in the presence of a catalytic amount of a ruthenium (IV) porphyrin complex catalyst, wherein the ruthenium (IV) porphyrin complex has the following structure:
- wherein M is a ruthenium (IV) porphyrin complex;
- wherein each R1-R12 is independently H, optionally substituted hydroxyl, optionally substituted amino, halogen, —CN, —NO2, optionally substituted C1-20 alkyl, optionally substituted phenyl;
- optionally substituted napthyl;
- optionally substituted anthracenyl, —SR13, —SO2R13, —CO2R13, and optionally substituted heteroatom-containing aromatic ring, in which the optional substituents are independently selected from the foregoing alkyl, phenyl, napthyl, anthracenyl and heteroatom-containing aromatic groups;
- R13 is independently selected from the same groups as R1 other than —SR13 and —SO2R13;
- and wherein L is a halogen molecule, solvent molecule, CO or R1.
A method for producing diazoacetate olefination from an unsaturated compound having one or more C═C functional groups, which comprises catalyzing the reaction of an oxidant with the unsaturated compound in the presence of a catalytic amount of a ruthenium (IV) porphyrin complex and adding a Lewis base and a diazo compound to the reaction, thereby producing an α, β-unsaturated ester of the diazoacetate olefination, wherein the ruthenium (IV) porphyrin complex has the following structure:
- wherein each R1-R12 is independently H, optionally substituted hydroxyl, optionally substituted amino, halogen, —CN, —NO2, optionally substituted C1-20 alkyl, optionally substituted phenyl;
- optionally substituted napthyl;
- optionally substituted anthracenyl, —SR13, —SO2R13, —CO2R13, and optionally substituted heteroatom-containing aromatic ring, in which the optional substituents are independently selected from the foregoing alkyl, phenyl, napthyl, anthracenyl and heteroatom-containing aromatic groups;
- R13 is independently selected from the same groups as R1 other than —SR13 and —SO2R13;
- wherein M is ruthenium;
- and
- wherein L is a halogen molecule, solvent molecule, CO or R1.
Dependencies are inferred from the claim text.