1,1'-Bis(diphenylphosphino)ferrocene

Reaction

1. Ligand for Pd-catalyzed cross-coupling.
2. Useful ligand for Pd-catalyzed carbon-nitrogen and carbon-oxygen bond forming procedures.
3. Ligand for Ni-catalyzed amination of aryl chlorides.
4. Ligand for Pd-catalyzed conversion of aryl halides to aryl nitriles.
5. Ligand for Ni-catalyzed Suzuki reactions.
6. Ni-catalyzed hydroamination of 1,3-dienes.
7. Pd-catalyzed hydrocarbonation and hydroamination of 3,3-dihexylcyclopropene.
8. Pd-catalyzed γ-arylation of β,γ-unsaturated ketones.
9. Ligand for Ru-catalyzed reduction of nitriles to primary amines.
10. Ligand for Rh-catalyzed alkyne head-to-tail dimerization.
11. Ligand for Rh-catalyzed cross-coupling
12. Ligand for Rh-catalyzed olefin isomerization
13. Ligand for Ni or Rh-catalyzed borylation
14. Ligand for regioselective Pd-catalyzed hydrophosphinylation of terminal alkynes to form branched alkenes.

Chemical Properties

1,1'-Bis(diphenylphosphino)ferrocene is deep yellow crystalline powder

Uses

1,1'-Bis(diphenylphosphino)ferrocene acts as a ligand in homogeneous catalysis. It is used as a ligand for ruthenium-catalyzed greener amine synthesis from amines and alcohols by hydrogen-borrowing. It is also employed as a ligand for Buchwald-Hartwig cross coupling. Further, it is used in the synthesis of coordination compound as well as the formation of complexes with various metals such as palladium chloride. In addition to this, it serves as a reagent for palladium-catalyzed coupling reactions and also plays an important role in Suzuki reaction.

Uses

1,1'-Bis(diphenylphosphino)ferrocene used coordination compound in synthesis, readily forms complexes with various metals, i.e. when reacting with the acetonitrile or benzonitrile complexes of PdCl2 it forms (dppf)PdCl2, which i s a popular reagent for palladium-catalyzed coupling reactions.

General Description

Novel functionalized furan derivatives were prepared via Pd-phosphine sequential C-C and C-O bond formation.

reaction suitability

reaction type: Cross Couplings
reagent type: ligand
reaction type: Buchwald-Hartwig Cross Coupling Reaction
reagent type: ligand
reaction type: Carbonylations
reagent type: ligand
reaction type: Ene Reaction
reagent type: ligand
reaction type: Heck Reaction
reagent type: ligand
reaction type: Negishi Coupling
reagent type: ligand
reaction type: Sonogashira Coupling
reagent type: ligand
reaction type: Stille Coupling
reagent type: ligand
reaction type: Suzuki-Miyaura Coupling
reagent type: ligand
reaction type: Tsuji-Trost Reaction

Synthesis

The general procedure for the synthesis of 1,1'-bis(diphenylphosphino)ferrocene (dppf) from the compound (CAS: 405164-68-3) is as follows: Example 4: 100 mg (0.171 mmol) of 1,1'-bis(diphenoxyphosphino)ferrocene was reacted with 4 mg (16 μmol) of I and 170 μL (0.68 mmol) of tributylphosphine in 1 mL of acetonitrile/THF (1:1, v/v) mixed solvent. The reaction mixture was stirred at room temperature for 10 min under nitrogen protection, followed by quenching the reaction with 100 μL of HO. The reaction was then quenched with 10 mL of ethyl acetate. The reaction mixture was diluted with 10 mL of ethyl acetate and washed three times (5 mL each) with saturated aqueous NaHCOsolution. The organic phase was dried with NaSO, filtered and concentrated under reduced pressure. The resulting residue was recrystallized with ethanol, the crystals were collected by filtration, washed and dried under vacuum to give 89 mg (0.160 mmol, 94% yield) of 1,1'-bis(diphenylphosphino)ferrocene (dppf).

Purification Methods

Wash it with distilled H2O and dry it in a vacuum. Dissolve it in ca 5 parts of hot dioxane and cool to give orange crystals m 181-183o. Recrystallisation from *C6H6/heptane (1:2) gives a product with m 183-184o. [Bishop et al. J Organomet Chem 27 241 1971.]

References

[1] Patent: WO2011/123037, 2011, A1. Location in patent: Page/Page column 23