((S)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl)dichloropalladium
[CAS# 127593-28-6]

Identification

• Classification: Organic raw materials >> Organic phosphine compound
• Name: ((S)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl)dichloropalladium
• Synonyms: BINAP-PdCl2
• Molecular Formula: C₄₄H₃₂Cl₂P₂Pd
• Molecular Weight: 800.00
• CAS Registry Number: 127593-28-6
• EC Number: 631-388-5
• SMILES: C1=CC=C(C=C1)P(C2=CC=CC=C2)C3=C(C4=CC=CC=C4C=C3)C5=C(C=CC6=CC=CC=C65)P(C7=CC=CC=C7)C8=CC=CC=C8.Cl[Pd]Cl

Properties

• Melting point: 230-300 ºC (decomp.) (Expl.)

Safety Data

• Hazard Symbols: GHS07 Warning
• Hazard Statements: H302-H312-H315-H319-H332-H335
• Precautionary Statements: P261-P264-P264+P265-P270-P271-P280-P301+P317-P302+P352-P304+P340-P305+P351+P338-P317-P319-P321-P330-P332+P317-P337+P317-P362+P364-P403+P233-P405-P501

Hazard Classification

Hazard	Class	Category Code	Hazard Statement
Specific target organ toxicity - single exposure	STOT SE	3	H335
Acute toxicity	Acute Tox.	4	H312
Skin irritation	Skin Irrit.	2	H315
Acute toxicity	Acute Tox.	4	H302
Acute toxicity	Acute Tox.	4	H332
Eye irritation	Eye Irrit.	2	H319
Skin sensitization	Skin Sens.	1	H317

Discovory and Applicatios

((S)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl)dichloropalladium, also known as (S)-BINAP-palladium(II) chloride, is an important chiral catalyst used extensively in organometallic chemistry, particularly in asymmetric catalysis. This compound consists of a palladium(II) center coordinated to the (S)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl ligand, which imparts chirality to the catalyst. Its significance lies in its ability to facilitate highly selective reactions that are crucial for the synthesis of chiral molecules, especially in the pharmaceutical and fine chemicals industries.

The development of BINAP-based palladium catalysts is closely tied to advancements in the field of asymmetric synthesis. The BINAP ligand was first introduced in the early 1980s, and its chiral nature allowed for the creation of palladium catalysts with the ability to selectively promote reactions leading to chiral products. This was a key development in synthetic organic chemistry because it opened up new possibilities for the efficient production of enantiomerically pure compounds, which are often required for pharmaceutical drugs.

The coordination of palladium to the (S)-BINAP ligand imparts a specific stereochemistry to the resulting catalyst, enabling the selective formation of one enantiomer over another in various reactions. The (S)-BINAP-palladium(II) chloride complex has been shown to catalyze several important reactions, including asymmetric hydrogenation, asymmetric cross-coupling, and the asymmetric alkylation of electrophilic compounds. These reactions are widely used in the synthesis of complex organic molecules, such as those found in medicinal chemistry and agrochemicals.

One of the most notable applications of ((S)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl)dichloropalladium is its role in the asymmetric hydrogenation of alkenes and imines. In this reaction, the palladium catalyst selectively adds hydrogen to one face of the substrate, creating a chiral product with high enantioselectivity. This is particularly valuable in the synthesis of chiral intermediates for pharmaceutical compounds, where the specific stereochemistry of the molecule is often crucial to its biological activity.

In addition to hydrogenation reactions, ((S)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl)dichloropalladium is also effective in catalyzing the Suzuki-Miyaura cross-coupling reaction. This reaction, which involves the coupling of aryl or vinyl boronic acids with halides, is widely used in the synthesis of biaryls and other important organic molecules. The (S)-BINAP-palladium catalyst enhances the selectivity and efficiency of the reaction, making it a valuable tool in the synthesis of complex organic materials and bioactive compounds.

Furthermore, the palladium catalyst is employed in other coupling reactions such as the Stille and Negishi reactions, which are important for the formation of carbon-carbon bonds in synthetic chemistry. These reactions are essential for building molecular architectures with specific properties and are widely applied in the preparation of pharmaceuticals, polymers, and other specialty chemicals.

The success of ((S)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl)dichloropalladium as a catalyst is attributed to the steric and electronic properties of the (S)-BINAP ligand. The ligand’s bulky and rigid structure, combined with its chiral centers, ensures that the palladium center is properly coordinated to the substrate in a way that favors the formation of a particular enantiomer. This highly selective catalytic behavior is a key reason why BINAP-based palladium catalysts are preferred in many asymmetric synthesis applications.

In summary, ((S)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl)dichloropalladium is a pivotal catalyst in modern organic chemistry. Its development has enabled the efficient and selective synthesis of chiral molecules, with far-reaching implications in the production of pharmaceuticals, agrochemicals, and advanced materials. Through its role in asymmetric hydrogenation, cross-coupling reactions, and other important synthetic transformations, this palladium catalyst remains an essential tool in both academic research and industrial applications.

References

2004. A highly efficient asymmetric Suzuki�Miyaura coupling reaction catalyzed by cationic chiral palladium(ii) complexes. Chemical Communications, (17).
DOI: 10.1039/B407250B

2015. Double [3 + 2]-dimerisation cascade synthesis of bis(triazolyl)bisphosphanes, a new scaffold for bidentate bisphosphanes. Dalton Transactions, 44(28).
DOI: 10.1039/C5DT02197A

2022. Aggregation-induced polarization (AIP) of derivatives of BINOL and BINAP. RSC Advances, 12(46).
DOI: 10.1039/D2RA05597J