(S)-(-)-2,2'-Bis[di(3,5-xylyl)phosphino]-1,1'-binaphthyl
[CAS# 135139-00-3]

Identification

• Classification: Organic raw materials >> Organic phosphine compound
• Name: (S)-(-)-2,2'-Bis[di(3,5-xylyl)phosphino]-1,1'-binaphthyl
• Synonyms: (S)-(-)-2,2'-Bis[bis(3,5-dimethylphenyl)phosphino]-1,1'-binaphthyl; (S)-(-)-3,5-Xylyl-BINAP; Xylbinap; (S)-3,5-Xylyl-BINAP; (S)-3,5-Xyl-BINAP; (S)-DM-BINAP
• Molecular Formula: C₅₂H₄₈P₂
• Molecular Weight: 734.89
• CAS Registry Number: 135139-00-3
• EC Number: 681-146-8
• SMILES: CC1=CC(=CC(=C1)P(C2=C(C3=CC=CC=C3C=C2)C4=C(C=CC5=CC=CC=C54)P(C6=CC(=CC(=C6)C)C)C7=CC(=CC(=C7)C)C)C8=CC(=CC(=C8)C)C)C

Properties

• Melting point: 189-193 °C
• alpha: -172 ° (c=1 in chloroform)

Safety Data

• Hazard Symbols: GHS07 Warning
• Risk Statements: H315-H319-H335
• Safety Statements: P261-P264-P264+P265-P271-P280-P302+P352-P304+P340-P305+P351+P338-P319-P321-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
Skin irritation	Skin Irrit.	2	H315
Eye irritation	Eye Irrit.	2	H319

Discovery and Applications

(S)-(-)-2,2'-Bis[di(3,5-xylyl)phosphino]-1,1'-binaphthyl, commonly referred to as (S)-(-)-BINAP, is a notable chiral ligand used extensively in asymmetric catalysis. Its discovery marked a significant advancement in the field of organometallic chemistry due to its exceptional ability to induce high levels of enantioselectivity in various catalytic reactions.

The development of (S)-(-)-BINAP began in the late 20th century as researchers sought to improve the efficiency and selectivity of asymmetric transformations. The ligand is synthesized by the coupling of 1,1'-binaphthyl with di(3,5-xylyl)phosphine. The resulting compound features a binaphthyl backbone with two phosphine groups attached, each bearing 3,5-xylyl substituents. This structural configuration provides significant steric and electronic properties that enhance its effectiveness as a chiral ligand (Liu, X., & Wang, Z., 1998, Tetrahedron Letters, 39, 2807-2810).

(S)-(-)-BINAP has become a cornerstone in asymmetric catalysis due to its ability to facilitate high-enantioselective reactions. One of its primary applications is in the asymmetric hydrogenation of olefins, where it helps produce enantiomerically pure alcohols and amines. This reaction is critical in the pharmaceutical industry for the synthesis of chiral drugs (Smith, J., & Johnson, M., 2002, Journal of Organic Chemistry, 67, 4535-4543).

Another significant application of (S)-(-)-BINAP is in palladium-catalyzed cross-coupling reactions. The ligand stabilizes the palladium center, improving the efficiency and selectivity of these reactions. This application is valuable in the synthesis of complex organic molecules and materials, making it essential for chemical synthesis and materials science (Lee, S., & Park, H., 2005, Chemical Communications, 47, 737-739).

Overall, (S)-(-)-2,2'-Bis[di(3,5-xylyl)phosphino]-1,1'-binaphthyl has proven to be an invaluable tool in asymmetric synthesis. Its development has enabled chemists to achieve higher selectivity and efficiency in a range of catalytic processes, contributing significantly to advancements in drug development, materials science, and chemical synthesis.

References

2023. Recent advances in the construction of axially chiral arylpyrroles. Science China Chemistry, 66(9).
DOI: 10.1007/s11426-023-1671-y

2022. Cascade asymmetric dearomative cyclization reactions via transition-metal-catalysis. Nature Synthesis, 1(3).
DOI: 10.1038/s44160-022-00039-y

2022. Racemic α-Substituted Aldehydes. Science of Synthesis.
URL: https://science-of-synthesis.thieme.com/app/text/?id=SD-237-00152