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Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions
Published on: March 20, 2014
Palladium-tetraphosphine complex: an efficient catalyst for the coupling of aryl halides with alkynes
Marie Feuerstein1, Florian Berthiol, Henri Doucet
1Laboratoire de Synthèse Organique associé au CNRS, Faculté des Sciences de Saint Jérôme, Avenue Escadrille Normandie-Niemen, 13397 Marseille Cedex 20, France.
A novel palladium catalyst system efficiently couples aryl halides and alkynes. This highly active catalyst achieved a turnover number of 2,600,000 for a specific reaction, demonstrating its potential in organic synthesis.
Area of Science:
- Organometallic Chemistry
- Catalysis
- Organic Synthesis
Background:
- Palladium-catalyzed cross-coupling reactions are fundamental in organic synthesis.
- Developing highly active and efficient catalysts is crucial for sustainable chemistry.
Purpose of the Study:
- To investigate the catalytic activity of a novel cyclopentane-palladium complex for aryl halide-alkyne coupling.
- To evaluate the efficiency and substrate-to-catalyst ratios achievable with this new catalytic system.
Main Methods:
- Synthesis and characterization of the cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)-cyclopentane-[PdCl(eta3-C3H5)]2 catalyst.
- Optimization of reaction conditions for the coupling of aryl halides with alkynes.
- Determination of catalyst activity, yield, and turnover number (TON).
Main Results:
- The catalyst system demonstrated high efficiency in coupling aryl halides with alkynes.
- Very high substrate-to-catalyst ratios were achieved.
- A remarkable turnover number of 2,600,000 was obtained for the reaction between 4-trifluoromethylbromobenzene and phenylacetylene.
Conclusions:
- The novel cyclopentane-palladium complex is a highly active catalyst for aryl halide-alkyne coupling.
- This catalyst enables efficient synthesis at low catalyst loadings, offering a significant advancement in cross-coupling methodologies.
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Preparation of Alkynes: Alkylation Reaction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Preparation of Alkynes: Dehydrohalogenation
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
Electrophilic Addition to Alkynes: Halogenation
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction

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