BINAP

BINAP
Names
	IUPAC name 2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl
	Other names BINAP
Identifiers
CAS Number	76189-55-4 (R) ; 76189-56-5 (S) ;
3D model (JSmol)	(Rac): Interactive image;
ChEMBL	ChEMBL1275990;
ChemSpider	551072 (Rac) ;
ECHA InfoCard	100.114.880
EC Number	616-304-7 619-338-0 616-305-2 918-620-3;
PubChem CID	634876 (+);
UNII	4F1X2F8NA3 (R) ; OX12238KWH (S) ;
CompTox Dashboard (EPA)	DTXSID40913327 ;
	InChI InChI=1S/C44H32P2/c1-5-19-35(20-6-1)45(36-21-7-2-8-22-36)41-31-29-33-17-13-15-27-39(33)43(41)44-40-28-16-14-18-34(40)30-32-42(44)46(37-23-9-3-10-24-37)38-25-11-4-12-26-38/h1-32H Key: MUALRAIOVNYAIW-UHFFFAOYSA-N ;
	SMILES (Rac): c1ccc(cc1)P(c2ccccc2)c3ccc4ccccc4c3c5c6ccccc6ccc5P(c7ccccc7)c8ccccc8;
Properties
Chemical formula	C44H32P2
Molar mass	622.688 g·mol−1
Appearance	Colorless solid
Melting point	239 to 241 °C (462 to 466 °F; 512 to 514 K) (R); 238–240 °C (S)
Solubility in water	organic solvents
Hazards
GHS pictograms
GHS Signal word	Warning
GHS hazard statements	H315, H319, H335, H413
GHS precautionary statements	P261, P264, P271, P273, P280, P302+352, P304+340, P305+351+338, P312, P321, P332+313, P337+313, P362, P403+233, P405, P501
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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	Infobox references

BINAP (2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) is an organophosphorus compound. This chiral diphosphine ligand is widely used in asymmetric synthesis. It consists of a pair of 2-diphenylphosphinonaphthyl groups linked at the 1 and 1′ positions. This C₂-symmetric framework lacks a stereogenic atom, but has axial chirality due to restricted rotation (atropisomerism). The barrier to racemization is high due to steric hindrance, which limits rotation about the bond linking the naphthyl rings. The dihedral angle between the naphthyl groups is approximately 90°. The natural bite angle is 93°.[1]

Ball and stick model of BINAP viewed as above

Use as ligand in asymmetric catalysis

BINAP is used in organic synthesis for enantioselective transformations catalyzed by its complexes of ruthenium, rhodium, and palladium.[2] As pioneered by Ryōji Noyori and his co-workers, rhodium complexes of BINAP are useful for the synthesis of (–)-menthol.[3][4]

Silver complexes are also important; BINAP-AgF can be used to enantioselectively protonate silyl enol ethers.[5]

Subsequent studies revealed that related diphosphines with a narrower dihedral angle between the aromatic faces give catalysts that are more enantioselective. One such ligand is SEGPHOS.[6]

Preparation

BINAP is prepared from BINOL[7][8] via its bistriflate derivatives. Both the (R)- and (S)-enantiomers, as well as the racemate, are commercially available. One of the wide applications include chemoselective hydrogenation, where BINAP is conjugated to rhodium.

References

Birkholz (née Gensow), Mandy-Nicole; Freixa, Zoraida; van Leeuwen, Piet W. N. M. (2009). "Bite angle effects of diphosphines in C–C and C–X bond forming cross coupling reactions". Chemical Society Reviews. 38 (4): 1099. doi:10.1039/B806211K. PMID 19421583.
Kitamura, Masato; M. Tokunaga; T. Ohkuma; R. Noyori (1998). "Asymmetric hydrogenation of 3-oxo carboxylates using BINAP-ruthenium complexes". Org. Synth. 9: 589.
Akutagawa, S (1992). "A practical synthesis of (−)-menthol with the Rh-BINAP catalyst". Chirality Ind.: 313–323.
Kumobayashi, Hidenori; Sayo, Noboru; Akutagawa, Susumu; Sakaguchi, Toshiaki; Tsuruta, Haruki (1997). "Industrial asymmetric synthesis by use of metal-BINAP catalysts". Nippon Kagaku Kaishi. 12: 835–846.
Yanagisawa, Akira; Touge, Taichiro; Takayoshi, Arai (2005). "Enantioselective Protonation of Silyl Enolates Catalyzed by a Binap⋅AgF Complex". Angewandte Chemie International Edition. 44 (10): 1546–8. doi:10.1002/anie.200462325.
Shimizu H, Nagasaki I, Matsumura K, Sayo N, Saito T (2007). "Developments in Asymmetric Hydrogenation from an Industrial Perspective". Acc. Chem. Res. 40 (12): 1385–1393. doi:10.1021/ar700101x. PMID 17685581.
"BINAP: An industrial approach to manufacture" (PDF). Rhodia. Retrieved 2008-10-20.
Cai, Dongwei; J. F. Payack; D. R. Bender; D. L. Hughes; T. R. Verhoeven; P. J. Reider (2004). "(R)-(+)- and (S)-(−)-2,2′-bis(diphenylphosphino)-1,1′-binapthyl (BINAP)". Org. Synth. 10: 112.

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[vanLeeuwen-1] Birkholz (née Gensow), Mandy-Nicole; Freixa, Zoraida; van Leeuwen, Piet W. N. M. (2009). "Bite angle effects of diphosphines in C–C and C–X bond forming cross coupling reactions". Chemical Society Reviews. 38 (4): 1099. doi:10.1039/B806211K. PMID 19421583.

[2] Kitamura, Masato; M. Tokunaga; T. Ohkuma; R. Noyori (1998). "Asymmetric hydrogenation of 3-oxo carboxylates using BINAP-ruthenium complexes". Org. Synth. 9: 589.

[3] Akutagawa, S (1992). "A practical synthesis of (−)-menthol with the Rh-BINAP catalyst". Chirality Ind.: 313–323.

[4] Kumobayashi, Hidenori; Sayo, Noboru; Akutagawa, Susumu; Sakaguchi, Toshiaki; Tsuruta, Haruki (1997). "Industrial asymmetric synthesis by use of metal-BINAP catalysts". Nippon Kagaku Kaishi. 12: 835–846.

[5] Yanagisawa, Akira; Touge, Taichiro; Takayoshi, Arai (2005). "Enantioselective Protonation of Silyl Enolates Catalyzed by a Binap⋅AgF Complex". Angewandte Chemie International Edition. 44 (10): 1546–8. doi:10.1002/anie.200462325.

[6] Shimizu H, Nagasaki I, Matsumura K, Sayo N, Saito T (2007). "Developments in Asymmetric Hydrogenation from an Industrial Perspective". Acc. Chem. Res. 40 (12): 1385–1393. doi:10.1021/ar700101x. PMID 17685581.

[7] "BINAP: An industrial approach to manufacture" (PDF). Rhodia. Retrieved 2008-10-20.

[8] Cai, Dongwei; J. F. Payack; D. R. Bender; D. L. Hughes; T. R. Verhoeven; P. J. Reider (2004). "(R)-(+)- and (S)-(−)-2,2′-bis(diphenylphosphino)-1,1′-binapthyl (BINAP)". Org. Synth. 10: 112.