Mapping the reaction pathway in palladium-catalyzed cross-coupling reactions
- Dyson Perrins Lab., Oxford (England)
The formation of the cyclooctatetraene (COT) complex Pd(dppf)(COT) (dppf = 1,1{prime}-bis(diphenylphosphino)ferrocene) from Pd(dppf)X{sub 2} (X = Cl, Sr, I) and dilithium cyclooctatetraenide in situ affords an entry into the cross-coupling chemistry of this system. The reaction of Pd(dppf)(COT) with an alkenyl bromide or iodide results in the formation of the appropriate ({eta}{sup 1}-alkenyl)palladium halide via an oxidative addition of a {eta}{sup 2}-coordinated alkene species. The full characterization of the intermediate Pd(dppf)(CH{double bond}CHC{sub 6}H{sub 4}OCHY{sub 3})Br (9) and the norbornene insertion product Pd(dppf)(C{sub 7}H{sub 10}CH{double bond}CHC{sub 6}H{sub 4}OCH{sub 3}) (15) is reported. A set of putative intermediates for the coupling of alkenyl and benzyl moieties by palladium complexes is demonstrated spectroscopically. The cross-coupling cycle for the case of alkenyl-aryl coupling is delineated by an analysis of cross-coupling reactions employing {sup 13}C-labeled catalysts and unlabeled substrates (and vice versa). Platinum analogues of all the intermediates in this cross-coupling catalytic cycle have been observed.
- OSTI ID:
- 7246131
- Journal Information:
- Organometallics; (USA), Journal Name: Organometallics; (USA) Vol. 9:2; ISSN 0276-7333; ISSN ORGND
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
CALCULATION METHODS
CATALYSIS
CHEMICAL REACTION KINETICS
COMPLEXES
COUPLING
DATA
DATA ANALYSIS
DIENES
EXPERIMENTAL DATA
FERROCENE
HYDROCARBONS
INFORMATION
IRON COMPLEXES
KINETICS
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
ORGANIC COMPOUNDS
PALLADIUM COMPLEXES
POLYENES
REACTION KINETICS
TRANSITION ELEMENT COMPLEXES