BiPhePhos

• CAS: 121627-17-6
• Catalog Number: ALC-FP-121627176
• Category: Featured Products
• Molecular Weight: 786.78
• Molecular Formula: C46H44O8P2
• Synonyms: 6,6'-[(3,3'-Di-tert-butyl-5,5'-dimethoxy-1,1'-biphenyl-2,2'-diyl)bis(oxy)]bis(dibenzo[d,f][1,3,2]dioxaphosphepin)
• Appearance: White powder
• Nuclear Magnetic Resonance: H-NMR: Conforms to structure
• Sample Lot No.: ANQSP3BK15AS

Case Study

BiPhePhos for the Application in Rhodium-Catalyzed Alkene Hydroformylation

Leidecker BN, et al. Catalysis Science & Technology, 2024, 14(14), 3966-3983.

High-pressure in situ FTIR and NMR spectroscopy were employed to investigate BiPhePhos-modified rhodium complexes under hydroformylation conditions. The experimental design combined reagent perturbations and chemometric peak group analysis to identify key resting-state species. The dominant hydrido complex e,e-[HRh(CO)₂(P∩P)] was observed after catalyst preformation and during n-regioselective hydroformylation. Minor dimerization occurred only under hydrogen depletion. Experiments revealed that mono- and dinuclear hydrido monocarbonyl complexes form at high ligand-to-metal ratios and low CO pressures, while bisphosphite acyl complexes exist as an equilibrium mixture. These methods provide precise structural insight into active catalytic species, enabling rational control of regioselectivity in alkene hydroformylation.

BiPhePhos for Kinetic Studies in 1-Dodecene Hydroformylation

Kiedorf G, et al. Chemical Engineering Science, 2014, 115, 31-48.

The kinetics of 1-dodecene hydroformylation were examined using a Rh-BiPhePhos catalyst in a thermomorphic solvent system. Batch reactors were charged with Rh(acac)(CO)₂, BiPhePhos, DMF, and decane, followed by ultrasonic mixing. After purging and pressurizing with CO/H₂, 1-dodecene was injected as a short pulse at ambient temperature. Samples were periodically collected over 1.5 h for analysis. Mechanistic kinetic models considered isomerization, hydrogenation, hydroformylation, and inactive Rh-species formation. Sequential network decomposition and model reduction using SVD enabled accurate parameter estimation. The experimental approach highlights BiPhePhos's role in controlling catalytic activity and selectivity under variable temperature and pressure conditions.

BiPhePhos for High-Selectivity Terminal Aldehyde Formation

Vogl C, et al. Journal of Molecular Catalysis A: Chemical, 2005, 232(1-2), 41-44.

BiPhePhos was applied in Rh-catalyzed hydroformylation of terminal and internal olefins to achieve high linear aldehyde selectivity. Reactions were conducted in 100 mL autoclaves under 30 bar syngas. Rh(CO)₂acac (4.5 μmol) and BiPhePhos (22.5 μmol) were dissolved in toluene with 45 mmol olefin, stirred at 1000 rpm, and heated to target temperature over 30 min. Following reaction, vessels were rapidly cooled, depressurized, and flushed for GC/GC-MS analysis. Conversions reached up to 99% with linear-to-branched ratios up to 99:1. This experimental setup demonstrates the practical utility of BiPhePhos in controlling regioselectivity and enabling efficient synthesis of terminal aldehydes under industrially relevant conditions.

BIPHEPHOS in Pd-Catalyzed S-Allylation of Thiols with High n-Regioselectivity

Schlatzer T, et al. Advanced Synthesis and Catalysis, 2020, 362(2), 331-336.

BIPHEPHOS was experimentally applied as a key bidentate phosphite ligand in a Pd-catalyzed S-allylation protocol for thiols, enabling highly n-selective formation of thioethers. In a typical method, thiol substrates were reacted with stable allyl carbonates or allyl acetates in the presence of a Pd(0) precursor and catalytic amounts of BIPHEPHOS under mild heating. The ligand effectively modulated the π-allyl-Pd intermediate, favoring linear over branched S-allylation. Reaction reversibility under the applied conditions was confirmed through mechanistic experiments. The protocol showed broad functional-group tolerance and was successfully extended to late-stage diversification of cephalosporin scaffolds, demonstrating BIPHEPHOS's practical value in selective sulfur-carbon bond construction.