321921-71-5 Usage
Description
Butyldi-1-adamantylphosphine is a bulky and electron-rich phosphine ligand that is highly effective for palladium-catalyzed cross-coupling reactions. It is a white to yellow solid with a melting point of 100°C and an estimated boiling point of 449.6±12.0°C. It is air-sensitive and should be stored at room temperature.
Uses
Used in Chemical Synthesis Industry:
Butyldi-1-adamantylphosphine is used as a ligand for palladium-catalyzed cross-coupling reactions such as Heck and Suzuki coupling, Buchwald-Hartwig amination of aryl chlorides, and α-arylation reactions of ketones. Its bulky and electron-rich nature makes it highly effective in these reactions.
Used in Catalyst Production:
Butyldi-1-adamantylphosphine is used in the production of CataCXium A, a catalyst for palladium-catalyzed cross-coupling reactions. CataCXium A is an electron-rich phosphine ligand that enhances the efficiency and selectivity of these reactions.
Other Applications:
Butyldi-1-adamantylphosphine is also used in various other palladium-catalyzed reactions, including:
1. Palladium-catalyzed carbonylation of aryl and heteroaryl halides
2. Palladium-catalyzed synthesis of (hetero)aromatic nitriles
3. Palladium-catalyzed aminocarbonylation of aryl halides
Butyldi-1-adamantylphosphine is sold in collaboration with Solvias AG.
Reaction
Ligand for the Pd-catalyzed Suzuki coupling reaction.
Ligand for the Pd-catalyzed formation of α-aryl ketones.
Ligand for the Pd-catalyzed aminations
Ligand for the Pd-catalyzed Heck reaction.
Ligand used for arylation of benzoic acids.
Ligand for the formylation of aryl bromides.
Ni-catalyzed denitrogenative alkyne insertion reactions of triazoles.
Ligand for palladium-catalyzed aminocarbonylation of aryl halides
Palladium-catalyzed direct arylation of oxazole at C-5 with aryl bromides, chlorides, and triflates
Palladium-catalyzed carbonylative sonogashira coupling of aryl bromides.
Synthesis
Phosphonium salt (2.2 mmol) was added to a cooled solution (- 78 °C) of
Et3N
(4.44 g, 44 mmol) in di-n-butyl ether (20 mL). The reaction mixture was
stirred at -78 °C for 5 h and then allowed to warm gradually to r.t.
The solvent was removed under vacuum and the residue was dissolved in
degassed EtOH (5 mL). After stirring for 15 min, the solid was filtered
off and dried to yield the desired phosphine, which can be further
purified by crystallization from EtOH. Butyldi-1-adamantylphosphine,
yield 90%. 31P NMR (C6D6)δ: 24.9. Mp 108-110°C. IR (KBr): 3425 (m, br),
2952 (s), 2847 (s), 2847 (s), 2675 (w), 1446 cm-1 (m). 1H NMR (250 MHz,
C6D6): δ = 0.96 (3 H, t, 3JH, H = 7.3 Hz, CH3), 1.35-2.03 (36 H, m,
adamantyl-30H, butyl-6H). 13C NMR (62 MHz, C6D6): δ = 41.3 (d, 2JC,P =
11.3 Hz, C-2), 37.4 (C-4), 36.1 (d, 1JC,P = 23.5 Hz, C-1), 33.9 (d,
1JC,P = 26.2 Hz, butyl-α -CH2), 29.1 (d, 3JC,P = 7.6 Hz, C-3), 24.9 (d,
2JC,P = 13.1 Hz, butyl-β -CH2), 17.1 (d, 3JC,P = 21.6 Hz, butyl-γ -CH2),
14.3 (butyl-CH3). MS (EI, 70 eV): m/z (%) = 358 (M+, 60), 135 (Ad+,
100).
Check Digit Verification of cas no
The CAS Registry Mumber 321921-71-5 includes 9 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 6 digits, 3,2,1,9,2 and 1 respectively; the second part has 2 digits, 7 and 1 respectively.
Calculate Digit Verification of CAS Registry Number 321921-71:
(8*3)+(7*2)+(6*1)+(5*9)+(4*2)+(3*1)+(2*7)+(1*1)=115
115 % 10 = 5
So 321921-71-5 is a valid CAS Registry Number.
InChI:InChI=1/C24H39P/c1-2-3-4-25(23-11-17-5-18(12-23)7-19(6-17)13-23)24-14-20-8-21(15-24)10-22(9-20)16-24/h17-22H,2-16H2,1H3
321921-71-5Relevant articles and documents
General and selective copper-catalyzed reduction of tertiary and secondary phosphine oxides: Convenient synthesis of phosphines
Li, Yuehui,Das, Shoubhik,Zhou, Shaolin,Junge, Kathrin,Beller, Matthias
supporting information; experimental part, p. 9727 - 9732 (2012/07/14)
Novel catalytic reductions of tertiary and secondary phosphine oxides to phosphines have been developed. Using tetramethyldisiloxane (TMDS) as a mild reducing agent in the presence of copper complexes, PO bonds are selectively reduced in the presence of other reducible functional groups (FGs) such as ketones, esters, and olefins. Based on this transformation, an efficient one pot reduction/phosphination domino sequence allows for the synthesis of a variety of functionalized aromatic and aliphatic phosphines in good yields.
Production of novel phosphane ligands and use in catalytical reactions
-
, (2008/06/13)
The invention relates to novel phosphane ligands of formula (Ia) and (Ib): (adamantyl)nP(alkyl)m(1a); (adamantyl)o(Alkyl)qP (alkylen′)P(adamantyl)r(alkyl)s (1b), wherein adamantyl represents an adamantyl radical (IIa, IIb) bonded to the phosphorous atom in position 1 or 2. The invention also relates to the production and use of the above-mentioned ligands in the presence of transitional metal compounds of the 8th. Subgroup of PSE for catalytic reactions, particularly for the refining of halogen aromatics for producing aryl olefins, dienes, diarylene, benzoic acid and acrylic acid derivatives, aryl alkanes and also amines.
A new efficient palladium catalyst for Heck reactions of deactivated aryl chlorides
Ehrentraut,Zapf,Beller
, p. 1589 - 1592 (2007/10/03)
A new palladium catalyst consisting of Pd(dba)2 and di-1-adamantyl-n-butylphosphine is described for the Heck reaction of non-activated and deactivated aryl chlorides. The new catalyst is more efficient and gives improved results compared to the previously known best catalyst system.
