321921-71-5

Basic information

• Product Name: CATACXIUM A
• Synonyms: CATACXIUM A;BUTYLDI-1-ADAMANTYLPHOSPHINE;nbutyl-di(1-adamantyl)phosphine;Di(1-adamantyl)-n-butylphosphine;Butyldi-1-adamantylphosphine,min.95%[cataCXiumA];BUTYLDI-1-ADAMANTYLPHOSPHINE [CATACXIUM A];cataCXium(R) A;Butyldi-1-adamantylphosphine ,95%
• CAS NO: 321921-71-5
• Molecular Formula: C₂₄H₃₉P
• Molecular Weight: 358.540221
• EINECS: 1312995-182-4
• Product Categories: organophosphine ligand;Achiral Phosphine;Aryl Phosphine
• Mol File: 321921-71-5.mol

Chemical Properties

• Melting Point: 100°C
• Boiling Point: 449.6 °C at 760 mmHg
• Flash Point: 239 °C
• Appearance: white to yellow/Powder
• Vapor Pressure: 7.51E-08mmHg at 25°C
• Storage Temp.: Inert atmosphere,Room Temperature
• Sensitive: air sensitive
• BRN: 8726448
• CAS DataBase Reference: CATACXIUM A(CAS DataBase Reference)
• NIST Chemistry Reference: CATACXIUM A(321921-71-5)
• EPA Substance Registry System: CATACXIUM A(321921-71-5)

Safety Data

• Safety Statements: 24/25
• WGK Germany: 3
• Hazardous Substances Data: 321921-71-5(Hazardous Substances Data)

Usage

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).

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

Upstream product

• 109-72-8 n-butyllithium 
• 157282-19-4 di-1-adamantylchlorophosphane 
• 542-69-8 1-iodo-butane 
• 131266-79-0 bis(1-adamantyl)phosphine oxide 
• 97580-87-5 (1-adamantyl)magnesium chloride 
• 594-19-4 tert.-butyl lithium 
• 109-65-9 1-bromo-butane 
• 131211-27-3 di-1-adamantylphosphine 
• 23906-91-4 (1-adamantyl)dichlorophosphine 
• 109-69-3 n-Butyl chloride 

Downstream Products

• 1005771-03-8 2-[3-(9,9-dimethyl-9H-fluoren-2-yl)phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 1375477-29-4 chloro[(di(1-adamantyl)-N-butylphosphine)-2-(2-aminobiphenyl)]palladium(II) 
• 1356681-77-0 9-{5-O-[bis(4-methoxyphenyl)(phenyl)methyl]-2-o-[4-(pyridin-4-yl)benzyl]-β-D-ribofuranosyl}-6-[2-(trimethylsilyl)ethoxy]-9H-purine 
• 1071965-84-8 PdBr(P(C₄H₉)(C₁₀H₁₅)2)2(COC₆H₄CF₃) 
• 1071965-74-6 PdBr(P(C₄H₉)(C₁₀H₁₅)2)2(C₆H₄CF₃) 
• 768-60-5 4-methoxyphenylacetylen 

Relevant articles and documents

General and selective copper-catalyzed reduction of tertiary and secondary phosphine oxides: Convenient synthesis of phosphines

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.

Palladium-catalyzed formylation of aryl bromides: Elucidation of the catalytic cycle of an industrially applied coupling reaction

The first comprehensive study of the catalytic cycle of the palladium-catalyzed formylation of aryl bromides with synthesis gas (CO/H 2, 1:1) is presented. The formylation in the presence of efficient (Pd/PR2nBu, R = 1-Ad, tBu) and nonefficient (Pd/PtBu3) catalysts was investigated. The main organometallic complexes involved in the catalytic cycle were synthesized and characterized, and their solution chemistry was studied in detail. Comparison of stoichiometric and catalytic reactions using P(1-Ad)2nBu, the most efficient ligand known for the formylation of aryl halides, led to two pivotal results: (1) The corresponding carbonylpalladium(O) complex [Pd n(CO)mLn] and the respective hydrobromide complex [Pd(Br)(H)L2] are resting states of the active catalyst, and they are not directly involved in the catalytic cycle. These complexes maintain the concentration of most active [PdL] species at a low level throughout the reaction, making oxidative addition the rate-determining step, and provide high catalyst longevity. (2) The product-forming step proceeds via base-mediated hydrogenolysis of the corresponding acyl complex, e.g., [Pd(Br)(p-CF 3C6H4CO){P(1-Ad)2 nBu}]2 (8), under mild conditions (25-50°C, 5 bar). Stoichiometric studies using the less efficient Pd/PtBu3 catalyst resulted in the isolation and characterization of the first stable three-coordinated neutral acylpalladium complex, [Pd(Br)(p-CF3C 6H4CO)(PtBu3)] (10). Hydrogenolysis of 10 needed significantly more drastic conditions compared to that of dimeric 8. In the presence of amine base, complex 10 gave a catalytically inactive diamino acyl complex, which explains the low activity of the Pd/P tBu3 catalyst formylation of aryl bromides.

Production of novel phosphane ligands and use in catalytical reactions

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.

General synthesis and catalytic applications of di(1-adamantyl) alkylphosphines and their phosphonium salts

An improved synthesis of di(1-adamantyl)alkylphosphines by alkylation of di(1-adamantyl)phosphine followed by deprotonation of the resulting phosphonium halide is described. Compared to previous protocols for the synthesis of this class of compounds, the procedure does not require chlorination of the secondary phosphine by phosgene, or formation of sensitive lithium di(1-adamantyl) phosphide. Selected examples of the prepared phosphonium salts and phosphines are shown to be excellent ligands for the palladium-catalyzed cross-coupling reaction of chloroarenes with arylboronic acids.

A new efficient palladium catalyst for Heck reactions of deactivated aryl chlorides

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.