Uses
tBuXPhos [2-Di-tert-butylphosphino-2′,4′,6′-triisopropylbiphenyl] is an air-stable, electron-rich biaryl phosphine ligand developed by the Buchwald group to enhance the reactivity of palladium catalysis during cross-coupling reactions. tBuXPhos has been used in the preparation of [tBuXPhosAu(MeCN)]BAr4F, a gold catalyst for the intermolecular [2+2] cycloaddition of terminal arylalkynes with substituted alkenes to form functionalized cyclobutenes with high regioselectivity.
tBuXPhos is a ligand for Pd-catalyzed C-O and C-N bond formation.
It can be used in the following reactions:
• Palladium-catalyzed Tsuji-Trost substitution and cross-coupling of benzylic fluorides.
• Palladium-catalyzed C-N cross-coupling of sulfinamides and aryl halides.
• Palladium-catalyzed rapid methoxylation and deuteriomethoxylation of bromo-chalcones.
Reactions
- Effective ligand for the Pd-catalyzed arylation of pyrazoles, indazoles and amino heterocycles.
- Ligand used in the Pd-catalyzed synthesis of phenols from aryl halides and KOH.
- Ligand used in the Pd-catalyzed of benzoic acids from aryl halides and CO2.
- Ligand used in the Pd-catalyzed trifluoromethylation of vinyl sulfonates.
- Ligand used in the Pd-catalyzed arylation of nitroacetates.
- Ligand used in the Pd-catalyzed Suzuki−Miyaura cross-coupling of allylboronates and aryl halides.
- Ligand used in the Pd-catalyzed cyanation of (hetero)arylchlorides and bromides.
- Ligand used in the Pd-catalyzed C–N cross coupling of sulfinamides and aryl halides.
- Ligand used in the Pd-catalyzed arylation of cyanamides.
Chemical Properties
White to pale yellow
Uses
tBuXPhos is a ligand for Pd-catalyzed C-O and C-N bond formation.
It can be used in the following reactions:
- Palladium-catalyzed Tsuji-Trost substitution and cross-coupling of benzylic fluorides.
- Palladium-catalyzed C-N cross-coupling of sulfinamides and aryl halides.
- Palladium-catalyzed rapid methoxylation and deuteriomethoxylation of bromo-chalcones.
Uses
Effective ligand for the Pd-catalyzed arylation of pyrazoles, indazoles and amino heterocycles
General Description
tBuXPhos
[2-Di-
tert-butylphosphino-2′,4′,6′-triisopropylbiphenyl] is an air-stable, electron-rich biaryl phosphine ligand developed by the Buchwald group to enhance the reactivity of palladium catalysis during cross-coupling reactions.
reaction suitability
reagent type: ligand
Synthesis
1. In a 1L three-necked flask, 32.5 g of 2-bromo-1,3,5-triisopropylbenzene, 5.6 g of magnesium shavings, and 300 mL of anhydrous tetrahydrofuran (THF) were added to prepare a Grignard reagent.
2. Under stirring, 20 g of 2-bromochlorobenzene was slowly added dropwise to the above solution to form 2,4,6-triisopropyl-2'-bromodiphenyl Grignard reagent, and the reaction was refluxed for 2 hours.
3. After completion of the reaction, cooled to room temperature, 2.4 g of tetrakis(triphenylphosphine)palladium was added as a catalyst and stirred for 30 minutes.
4. At room temperature, 18.8 g of di-tert-butylphosphonium chloride was slowly added dropwise to the reaction mixture and the reaction was continued at reflux for 5 hours.
5. The reaction mixture was cooled in an ice water bath and 200 mL of saturated aqueous ammonium chloride solution was slowly added dropwise to quench the reaction.
6. The organic phase was separated and crystallized by addition of methanol and filtered to afford 41.7 g of the white solid product 2-di-tert-butylphosphino-2',4',6'-triisopropylbiphenyl in 94% yield.
References
[1] Patent: CN105859774, 2016, A. Location in patent: Paragraph 0078; 0079; 0080; 0081
[2] Journal of the American Chemical Society, 2003, vol. 125, # 22, p. 6653 - 6655
