DIOP

DIOP
Names
IUPAC name
O-Isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane
Preferred IUPAC name
{[(4R,5R)-2,2-Dimethyl-1,3-dioxolane-4,5-diyl]bis(methylene)}bis(diphenylphosphane)
Other names
(−)-2,3-O-Isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane

(−)-1,4-Bis(diphenylphosphino)-1,4-dideoxy-2,3-O-isopropylidene-L-threitol
(+)-2,3-O-Isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane

(+)-1,4-Bis(diphenylphosphino)-1,4-dideoxy-2,3-O-isopropylidene-L-threitol
Identifiers
3D model (JSmol)
ChemSpider
UNII
  • (–): InChI=1S/C31H32O2P2/c1-31(2)32-29(23-34(25-15-7-3-8-16-25)26-17-9-4-10-18-26)30(33-31)24-35(27-19-11-5-12-20-27)28-21-13-6-14-22-28/h3-22,29-30H,23-24H2,1-2H3/t29-,30-/m0/s1
    Key: VCHDBLPQYJAQSQ-KYJUHHDHSA-N
  • (–): CC1(O[C@H]([C@@H](O1)CP(c2ccccc2)c3ccccc3)CP(c4ccccc4)c5ccccc5)C
Properties
C31H32O2P2
Molar mass 498.543 g·mol−1
Appearance White solid
Melting point 86 to 89 °C (187 to 192 °F; 359 to 362 K)
Insoluble
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

DIOP (2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane) is an organophosphorus compound that is used as a chiral ligand in asymmetric catalysis. It is a white solid that is soluble in organic solvents.

DIOP is prepared from the acetonide of d,l-tartaric acid, which is reduced prior to attachment of the PPh2 substituents.

Use

The DIOP ligand binds to metals via conformationally flexible seven-membered C4P2M chelate ring.[1][2]

DIOP is a historically important in the development of ligands for use in asymmetric catalysis, an atom-economical method for the preparation of chiral compounds. Described in 1971, it was the first example of a C2-symmetric diphosphine.[3] Its complexes have been applied to the reduction of prochiral olefins, ketones, and imines. Knowles et al. independently reported the related C2-symmetric diphosphine DIPAMP.[1]

Since the discovery of DIOP, many analogues of DIOP have been introduced. These DIOP derivatives include MOD-DIOP, Cy-DIOP, DIPAMP, and DBP-DIOP. Out of many derivatives, DBP-DIOP exhibits good regio- and enantioselectivity in the hydroformylation of butenes and styrene. DIOP was the first chiral ligand used in the platinum-tin-catalyzed hydroformylation. The reactivity, chemo – and the enantioselectivity of DIOP is influenced by CO and H2 pressure and polarity of the solvents. The best results in asymmetric hydroformylation are achieved in solvents with medium polarity: benzene and toluene.[2]

References

  1. ^ a b Shang, G.; Li, W.; Zhang, X. (2010). "Transition Metal-Catalyzed Homogeneous Asymmetric Hydrogenation". In Iwao Ojima (ed.). Catalytic Asymmetric Synthesis (3rd ed.). New York: John Wiley & Sons. pp. 343–436.
  2. ^ a b Agbossou, F.; Carpentier, J.; Mortreux, A. (1995). "Asymmetric Hydroformylation". Chem. Rev. 95 (7): 2485–2806. doi:10.1021/cr00039a008.
  3. ^ Dang, T. P.; Kagan, H. B. (1971). "The asymmetric synthesis of hydratropic acid and amino-acids by homogeneous catalytic hydrogenation". Journal of the Chemical Society D: Chemical Communications (10): 481. doi:10.1039/C29710000481.

Content Disclaimer

Informasi ini disarikan dari Wikipedia dan disajikan kembali untuk tujuan edukasi. Konten tersedia di bawah lisensi CC BY-SA 3.0. Kami tidak bertanggung jawab atas ketidakakuratan data yang bersumber dari kontribusi publik tersebut.

  1. The information displayed on this website is sourced in part or in whole from Wikipedia and has been adapted for the purpose of restating it. We strive to provide accurate and relevant information, however:
  2. There is no guarantee of absolute accuracy. Wikipedia is an open, collaborative project that can be edited by anyone, so information is subject to change.
  3. It is not intended to constitute professional advice. The content displayed is for informational and educational purposes only. For important decisions (e.g., medical, legal, or financial), please consult a professional.
  4. Content copyright. Wikipedia is licensed under the Creative Commons Attribution-ShareAlike License (CC BY-SA). This means that content may be reused with appropriate attribution and shared under a similar license.
  5. Responsible use. Any risk arising from the use of information from this website is entirely the responsibility of the user.