| BINAP | |
|---|---|
 |
|
| IUPAC name |
2,2'-bis(diphenylphosphino)-1,1'-binaphthyl
|
| Other names | BINAP |
| Identifiers | |
| CAS number | 76189-55-4,(R) 76189-56-5 (S) |
| Properties | |
| Molecular formula | C44H32P2 |
| Molar mass | 622.67 g/mol |
| Appearance | colorless solid |
| Melting point |
239-241 °C (R), 238-240 °C (S) |
| Solubility in water | organic solvents |
| Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) | |
| Infobox references | |
BINAP is an abbreviation for the organophosphorus compound 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl. This chiral ligand is widely used in asymmetric synthesis. It consists of a pair of 2-diphenylphosphinonaphthyl groups linked at the 1 and 1´ positions (Figure 1). This C2-symmetric framework lacks stereogenic atom (see axial chirality). The barrier to racemization is high due to steric hindrance that limits rotation about the bond linking the naphthyl rings (see atropisomer). The dihedral angle is approximately 90˚.
BINAP is used in organic synthesis for enantioselective transformations catalyzed by its complexes of ruthenium, rhodium, and palladium[1]. As pioneered by Ryoji Noyori and his co-workers, Rh complexes of BINAP are useful for the synthesis of (-)-menthol.[2][3]
This synthetic method was industrialized by Takasago International Corporation. In part for this work, Ryoji Noyori was awarded the 2001 Nobel Prize in Chemistry.
BINAP is prepared from BINOL[4][5] (1,1'-bi-2-naphthol) via its bis-triflate derivatives. Both the R and S enantiomers as well as the racemate are commercially available.
BINOL can be reacted with chlorodiphenylphosphine to make phosphinous acid, diphenyl-[1,1'-binaphthalene]-2-2'-diyl ester (BINAPO)[6]
References
- ^ Kitamura, Masato; M. Tokunaga, T. Ohkuma, and R. Noyori (1998). "Asymmetric hydrogenation of 3-oxo carboxylates using BINAP-ruthenium complexes". Org. Syn. 9: 589. http://www.orgsynth.org/orgsyn/prep.asp?prep=cv9p0589.
- ^ 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; and Tsuruta, Haruki (1997). "Industrial asymmetric synthesis by use of metal-BINAP catalysts". Nippon Kagaku Kaishi 12: 835−846.
- ^ "BINAP: An industrial approach to manufacture". Rhodia (company). http://www.rhodia-phosphines.com/docs/Rhodia.pdf. Retrieved 2008-10-20.
- ^ Cai, Dongwei; J. F. Payack, D. R. Bender, D. L. Hughes, T. R. Verhoeven, and P. J. Reider (2004). "(R)-(+)- and (S)-(−)-2,2'-bis(diphenylphosphino)-1,1'-binapthyl (BINAP)". Org. Syn. 10: 112. http://www.orgsynth.org/orgsyn/prep.asp?prep=v76p0006.
- ^ Nakajima, Makoto; S. Kotani, T. Ishizuka, S. Hashimoto (2005). "Chiral Phosphine Oxide BINAPO as a Catalyst for Enantioselective Allylation of Aldehydes with Allyltrichlorosilanes". ChemInform. doi:.
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