(+)-DIOP

Base Information

• Chemical Name: (+)-DIOP
• CAS No.: 37002-48-5
• Molecular Formula: C31H32O2P2
• Molecular Weight: 498.541
• Hs Code.: 29319090
• European Community (EC) Number: 253-307-9
• UNII: 5P52K0IJ7T
• DSSTox Substance ID: DTXSID001119711
• Nikkaji Number: J17.482C
• Wikidata: Q27262677
• Mol file: 37002-48-5.mol

Synonyms:Phosphine,[[(4S,5S)-2,2-dimethyl-1,3-dioxolane-4,5-diyl]bis(methylene)]bis[diphenyl-(9CI);(+)-2,3-O-Isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane;(+)-4,5-Bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxolane;(+)-DIOP;(4S,5S)-4,5-Bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxolane;(S)-DIOP;(S,S)-4,5-Bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxolane;(S,S)-DIOP;DIOP, (+)-;[[(4S,5S)-2,2-Dimethyl-1,3-dioxolane-4,5-diyl]bis(methylene)]bis[diphenylphosphine];

Chemical Property of (+)-DIOP

Chemical Property:

• Appearance/Colour: white powder
• Vapor Pressure: 2.75E-13mmHg at 25°C
• Melting Point: 86-88 °C(lit.)
• Boiling Point: 590.3 °C at 760 mmHg
• Flash Point: 390.9 °C
• PSA: 45.64000
• LogP: 5.77230
• Storage Temp.: 0-6°C
• Sensitive.: Air Sensitive
• Water Solubility.: Sparingly soluble in water at 25°C 2.1E-5 g/L.
• XLogP3: 6.2
• Hydrogen Bond Donor Count: 0
• Hydrogen Bond Acceptor Count: 2
• Rotatable Bond Count: 8
• Exact Mass: 498.18775425
• Heavy Atom Count: 35
• Complexity: 528

Purity/Quality:

97% ^*data from raw suppliers

(2S,3S)-(+)-1,4-Bis(diphenylphosphino)-2,3-O-isopropylidene-2,3-butanediol ^*data from reagent suppliers

Safty Information:

• Pictogram(s): Xi
• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26

MSDS Files:

SDS file from LookChem

Total 1 MSDS from other Authors

Useful:

• Canonical SMILES: CC1(OC(C(O1)CP(C2=CC=CC=C2)C3=CC=CC=C3)CP(C4=CC=CC=C4)C5=CC=CC=C5)C
• Isomeric SMILES: CC1(O[C@@H]([C@H](O1)CP(C2=CC=CC=C2)C3=CC=CC=C3)CP(C4=CC=CC=C4)C5=CC=CC=C5)C
• General Description: (+)-DIOP is a chiral diphosphine ligand used in asymmetric catalysis, particularly in the enantioselective hydrogenation of prochiral olefins when complexed with Rh(I). It demonstrates high enantioselectivity and can be effectively immobilized on porous silica via hydrogen bonding, forming a recyclable heterogeneous catalyst without significant loss of activity or metal leaching. This immobilization strategy provides a practical alternative to covalent attachment methods while maintaining catalytic performance.

Technology Process of (+)-DIOP

There total 5 articles about (+)-DIOP which guide to synthetic route it. The literature collected by LookChem mainly comes from the sharing of users and the free literature resources found by Internet computing technology. We keep the original model of the professional version of literature to make it easier and faster for users to retrieve and use. At the same time, we analyze and calculate the most feasible synthesis route with the highest yield for your reference as below:

synthetic route:

Reference yield: 8.0%

sodium diphenylphosphide (4376-01-6) + 1,4-di-o-tosyl-2,3-isopropylidene-D-threitol (51064-65-4) → (S,S)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane (37002-48-5) + Toluene-4-sulfonic acid (4R,5S)-5-[(diphenylphosphanyl)-methyl]-2,2-dimethyl-[1,3]dioxolan-4-ylmethyl ester

Guidance literature:

In tetrahydrofuran; for 6h; Heating;

DOI:10.1016/0022-328X(88)80191-8

Reference yield:

→ (S,S)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane (37002-48-5)

Guidance literature:

Reference yield:

diphenylphosphane (829-85-6) → (+/-)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane (32305-98-9,37002-48-5,50763-75-2,53531-20-7,55056-79-6,119479-50-4,136655-45-3)

Guidance literature:

Multi-step reaction with 2 steps

1.1: n-BuLi / tetrahydrofuran; hexane / 4 h / -35 °C

1.2: tetrahydrofuran; hexane / 5 h / 0 °C

2.1: 2.5 g / p-toluenesulfonic acid / benzene / 0.5 h / Heating

With n-butyllithium; toluene-4-sulfonic acid; In tetrahydrofuran; hexane; benzene;

DOI:10.1021/ja045981k

upstream raw materials:

sodium diphenylphosphide

1,4-di-o-tosyl-2,3-isopropylidene-D-threitol

2,2-dimethoxy-propane

diphenylphosphane

Downstream raw materials:

(+)-(S,S)-2,3-dihydroxy-1,4-bis(diphenylphosphino)-butane

(4R,5R)-4,5-Bis-(diphenyl-phosphinoylmethyl)-2,2-dimethyl-[1,3]dioxolane

(anti-2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene)bis(diphenylphosphine oxide)

{Rh((+)-diop)Cl}

Refernces

Immobilization of Optically Active Rhodium-Diphosphine Complexes on Porous Silica via Hydrogen Bonding

10.1002/1615-4169(20010129)343:1<41::AID-ADSC41>3.0.CO;2-P

The research explores an innovative method for immobilizing optically pure Rh(I)-diphosphine complexes on porous silica through hydrogen bonding interactions, aiming to create heterogeneous catalysts for the enantioselective hydrogenation of prochiral olefins. The study successfully immobilized various complexes, including [(R)-(R)-BDPBzPSOs]Rh(nbd) (1), [(+)-DIOP]Rh(nbd)OTf (2), and [(S)-BINAP]Rh(nbd)OTf (3), using a straightforward solvent impregnation technique. The immobilized catalysts retained their enantioselectivity and demonstrated effective recyclability without significant loss of activity or rhodium leaching. Key chemicals used in the research include the chiral ligands [(R)-(R)-BDPBzPSOs], (+)-DIOP, and (S)-BINAP, along with [Rh(nbd)Cl]? as the rhodium precursor. The study concludes that hydrogen-bonded immobilization is a viable strategy for creating efficient and recyclable enantioselective catalysts, offering a simpler alternative to traditional covalent grafting methods.