(S)-2,2'-Bis[bis(4-methylphenyl)phosphino]-1,1'-binaphthyl
[CAS# 100165-88-6]

Identification

• Classification: Chemical reagent >> Organic reagent >> Polycyclic compound
• Name: (S)-2,2'-Bis[bis(4-methylphenyl)phosphino]-1,1'-binaphthyl
• Synonyms: (S)-(-)-2,2'-Bis[di(p-tolyl)phosphino]-1,1'-binaphthyl; (S)-4-Me-BINAP; (S)-Tol-BINAP; 1,1'-(1S)-[1,1'-Binaphthalene]-2,2'-diylbis[1,1-bis(4-methylphenyl)phosphine
• Molecular Formula: C₄₈H₄₀P₂
• Molecular Weight: 678.79
• CAS Registry Number: 100165-88-6
• EC Number: 623-900-0
• SMILES: CC1=CC=C(C=C1)P(C2=CC=C(C=C2)C)C3=C(C4=CC=CC=C4C=C3)C5=C(C=CC6=CC=CC=C65)P(C7=CC=C(C=C7)C)C8=CC=C(C=C8)C

Properties

• Boiling Point: 255-257 °C
• Boiling Point: 754.4±60.0 °C (760 mmHg), Calc.^*
• Flash Point: 438.8±39.2 °C, Calc.^*

^* Calculated using Advanced Chemistry Development (ACD/Labs) Software.

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
Self-heating substances or mixtures	Self-heat.	2	H252
Flammable solids	Flam. Sol.	2	H228

Discovery and Applications

(S)-2,2'-Bis[bis(4-methylphenyl)phosphino]-1,1'-binaphthyl, commonly referred to as (S)-BINAP, is a pivotal chiral ligand in asymmetric catalysis. This compound has played a crucial role in the development of highly enantioselective processes, making it a cornerstone in the field of organic synthesis.

The discovery of (S)-BINAP dates back to the 1980s when it was first synthesized by the research group of Ryoji Noyori, a Nobel laureate in Chemistry. Noyori and his team were investigating ways to improve the selectivity and efficiency of chiral catalysts used in asymmetric hydrogenation reactions. Their efforts led to the creation of (S)-BINAP, a compound that quickly gained recognition for its outstanding performance as a chiral ligand.

Structurally, (S)-BINAP consists of a binaphthyl backbone with two bis(4-methylphenyl)phosphino groups attached at the 2,2' positions. This unique structure imparts significant steric hindrance and electronic properties to the ligand, which are crucial for its effectiveness in catalysis. The chiral nature of (S)-BINAP enables it to induce asymmetry in catalytic reactions, leading to the production of enantiomerically pure compounds.

One of the most prominent applications of (S)-BINAP is in asymmetric hydrogenation, where it serves as a ligand for transition metal catalysts, particularly rhodium and ruthenium complexes. These catalytic systems have been employed in the synthesis of various chiral molecules, including pharmaceuticals, agrochemicals, and fine chemicals. The high enantioselectivity achieved with (S)-BINAP-based catalysts has made it possible to produce enantiopure compounds on an industrial scale.

In addition to asymmetric hydrogenation, (S)-BINAP has found applications in other asymmetric catalytic processes, such as allylic substitution, hydroboration, and cyclopropanation reactions. Its versatility as a chiral ligand has made it a valuable tool in the toolbox of synthetic chemists, enabling the efficient synthesis of a wide range of chiral molecules.

The impact of (S)-BINAP on the field of asymmetric catalysis cannot be overstated. It has not only facilitated the development of new catalytic processes but also contributed to the advancement of green chemistry by enabling more sustainable and efficient synthetic methods. The success of (S)-BINAP has inspired the design and synthesis of numerous other chiral ligands, further expanding the possibilities of asymmetric catalysis.

In summary, the discovery of (S)-2,2'-Bis[bis(4-methylphenyl)phosphino]-1,1'-binaphthyl has been a milestone in the field of asymmetric catalysis. Its application as a chiral ligand has revolutionized the synthesis of enantiopure compounds, making it an indispensable tool in both academic research and industrial production.

References

2003. Mechanism of Asymmetric Hydrogenation of Ketones Catalyzed by BINAP/1,2-Diamine-Ruthenium(II) Complexes. Journal of the American Chemical Society, 125(42).
DOI: 10.1021/ja030272c

2013. Iridium-Catalyzed Asymmetric Ring-Opening of Oxabicyclic Alkenes with Carboxylic Acids. Catalysis Letters, 143(12).
DOI: 10.1007/s10562-013-1136-x

2018. Palladium-Catalysed Construction of All-Carbon Quaternary Centres with Propargylic Electrophiles: Challenges in the Simultaneous Control of Regio-, Chemo- and Enantioselectivity. Synthesis, 50(16).
DOI: 10.1055/s-0036-1591957