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BINAP
Names
Preferred IUPAC name
([1,1′-Binaphthalene]-2,2′-diyl)bis(diphenylphosphane)
Other names
BINAP
Identifiers
3D model ( JSmol)
ChEMBL
ChemSpider
ECHA InfoCard 100.114.880 Edit this at Wikidata
EC Number
  • 616-304-7

    619-338-0 616-305-2

    918-620-3
PubChem CID
UNII
  • 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 ☒N
    Key: MUALRAIOVNYAIW-UHFFFAOYSA-N ☒N
  • (Rac): c1ccc(cc1)P(c2ccccc2)c3ccc4ccccc4c3c5c6ccccc6ccc5P(c7ccccc7)c8ccccc8
Properties
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)
organic solvents
Hazards
GHS labelling:
GHS07: Exclamation mark
Warning
H315, H319, H335, H413
P261, P264, P271, P273, P280, P302+P352, P304+P340, P305+P351+P338, P312, P321, P332+P313, P337+P313, P362, P403+P233, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N  verify ( what is checkY☒N ?)
Ball and stick model of BINAP viewed as above

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-diphenylphosphino naphthyl 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]

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 bis triflate 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.

Further reading

  • Berthod, Mikaël; Mignani, Gérard; Woodward, Gary; Lemaire, Marc (2005). "Modified BINAP: The How and the Why". Chemical Reviews. 105 (5): 1801–1836. doi: 10.1021/cr040652w. PMID  15884790.
  • Genet, Jean-Pierre; Ayad, Tahar; Ratovelomanana-Vidal, Virginie (2014). "Electron-Deficient Diphosphines: The Impact of DIFLUORPHOS in Asymmetric Catalysis". Chemical Reviews. 114 (5): 2824–2880. doi: 10.1021/cr4003243. PMID  24517862.
  • Kočovský, Pavel; Vyskočil, Štěpán; Smrčina, Martin (2003). "Non-Symmetrically Substituted 1,1'-Binaphthyls in Enantioselective Catalysis". Chemical Reviews. 103 (8): 3213–3246. doi: 10.1021/cr9900230. PMID  12914496.
  • Zhang, Zhenfeng; Butt, Nicholas A.; Zhang, Wanbin (2016). "Asymmetric Hydrogenation of Nonaromatic Cyclic Substrates". Chemical Reviews. 116 (23): 14769–14827. doi: 10.1021/acs.chemrev.6b00564. PMID  27960269.
  • Clevenger, Andrew L.; Stolley, Ryan M.; Aderibigbe, Justis; Louie, Janis (2020). "Trends in the Usage of Bidentate Phosphines as Ligands in Nickel Catalysis". Chemical Reviews. 120 (13): 6124–6196. doi: 10.1021/acs.chemrev.9b00682. PMID  32491839. S2CID  219311508.

References

  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): 1099–1118. 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 (12): 835–846. doi: 10.1246/nikkashi.1997.835.
  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. PMID  15645475.
  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 (1999). "(R)-(+)- and (S)-(−)-2,2′-bis(diphenylphosphino)-1,1′-binapthyl (BINAP)". Organic Syntheses. 76: 6.
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