32305-98-9

Basic information

• Product Name: (-)-DIOP
• Synonyms: (2r,3r)-(-)-1,4-Bis(Diphenyl;(-)-2,3-O-Isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane, 98% 1GR;(4R,5R)-(-)-4,5-Bis(diphenylphosphinoMethyl)-2,2-diMethyl-1,3-dioxolane,99% (R,R)-DIOP;(4R,5R)-(-)-Bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxolane (-)-DIOP (2R,3R)-(-)-2,3-O-Isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane;)-2,3-O-Isopropylidene-2,3-dihydroxy-1,4-bis(dipheny;(4R,5R)-(-)-2,2-Dimethyl-4,5-bis((diphenylphosphino)methyl)-1,3-dioxolane;(4R,5R)-(-)-4,5-Bis(diphenylphosphinoMethyl)-2,2-diMethyl-1,3-dioxolane,(R,R)-DIOP.;(4R,5R)-(-)-4,5-BIS(DIPHENYLPHOSPHINOMET
• CAS NO: 32305-98-9
• Molecular Formula: C₃₁H₃₂O₂P₂
• Molecular Weight: 498.53
• EINECS: 250-984-2
• Product Categories: organophosphine ligand;DIOP Series;Chiral Phosphine;Asymmetric Synthesis;Dioxanes & Dioxolanes;Dioxolanes;Phosphine Ligands;Synthetic Organic Chemistry
• Mol File: 32305-98-9.mol

Chemical Properties

• Melting Point: 88-90 °C(lit.)
• Boiling Point: 590.3 °C at 760 mmHg
• Flash Point: 390.9 °C
• Appearance: white/Powder
• Vapor Pressure: 2.75E-13mmHg at 25°C
• Storage Temp.: 0-6°C
• Sensitive: Air Sensitive
• BRN: 1441045
• CAS DataBase Reference: (-)-DIOP(CAS DataBase Reference)
• NIST Chemistry Reference: (-)-DIOP(32305-98-9)
• EPA Substance Registry System: (-)-DIOP(32305-98-9)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36/37
• WGK Germany: 3
• F: 10-23
• TSCA: No
• Hazardous Substances Data: 32305-98-9(Hazardous Substances Data)

Usage

Uses

Used in Pharmaceutical Industry:
(-)-DIOP is used as a chiral ligand for the in situ preparation of chiral hydrogenation catalysts, which are essential in the synthesis of enantiomerically pure compounds. This application is particularly important in the production of pharmaceuticals, where the desired biological activity is often associated with a specific enantiomer.
Used in Chemical Synthesis:
(-)-DIOP is used as a ligand in asymmetric catalysis for the synthesis of various chiral compounds, including natural products, agrochemicals, and other specialty chemicals. Its ability to induce high enantioselectivity makes it a valuable tool in the development of enantiomerically pure products.
Used in Research and Development:
(-)-DIOP is utilized in academic and industrial research settings to explore new methods and improve existing processes in asymmetric catalysis. Its unique properties allow chemists to investigate novel reaction pathways and develop more efficient and selective catalytic systems.

Purification Methods

It has been recrystallised from *C6H6/pet ether. After 2 recrystallisations from EtOH, it was pure by TLC on silica gel using Me2CO/hexane as solvent. [Kagan & Dang J Am Chem Soc 94 6429 1972.] Lanthanide shift reagents See in “Aliphatic Compounds”, Chapter 4, europium (III) acetate above and Eu(tmc)3 and Eu(tfc)3 below.

InChI:InChI=1/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

Upstream product

• 4248-74-2 ((4S,5S)-2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene) dimethanesulfonate 
• 99436-45-0 (2R,3R)-1,4-bis(diphenylphosphino)-2,3-dihydroxy-2,3-O-isopropylidnebutane P,P'-dioxide 
• 69055-79-4 (+)-(2R,3R)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-dichlorobutane 
• 829-85-6 diphenylphosphane 
• 59779-75-8 diethyl (4R,5R)-2,2-dimethyl-1,3-dioxolane-4,5-dicarboxylate 
• 4376-01-6 sodium diphenylphosphide 
• 37002-45-2 (4S,5S)-2,2-dimethyl-4,5-bis(p-toluenesulfonyloxymethyl)-1,3-dioxolan 
• 37031-29-1 (-)-dimethy-2,3-O-isopropylidene-L-tartrate 
• 77-76-9 2,2-dimethoxy-propane 
• 82449-88-5 (2S,3S)-2,3-o-isopropylidene-2,3-dihydroxy-1,4-(diphenylphosphinoxy)bitane 
• 50622-09-8 2,3-O-isopropylidene-L-threitol 
• 135218-43-8 (2R,3R)-(-)-1,4-bis(diphenylphosphino)-2,3-butane-diol 
• 65567-06-8 lithium diphenylphosphide 

Downstream Products

• 70341-07-0 {RhCl(4R,5R-DIOP)} 

Relevant articles and documents

High linear selectivity ligand for allyl alcohol hydroformylation

A process for selectively producing 4-hydroxybutyraldehyde from allyl alcohol is described. The process comprises reacting allyl alcohol with a mixture of carbon monoxide and hydrogen in the presence of a solvent and a catalyst system comprising a rhodium complex and a trans-1,2-bis(bis(3,4,5-tri-n-alkylphenyl)phosphinomethyl)-cyclobutane. The process gives high yield of 4-hydroxybutyraldehyde compared to temperature.

Palladium- and Rhodium-Catalyzed Dynamic Kinetic Resolution of Racemic Internal Allenes Towards Chiral Pyrazoles

A complementing Pd- and Rh-catalyzed dynamic kinetic resolution (DKR) of racemic allenes leading to N-allylated pyrazoles is described. Such compounds are of enormous interest in medicinal chemistry as certified drugs and potential drug candidates. The new methods feature high chemo-, regio- and enantioselectivities aside from displaying a broad substrate scope and functional group compatibility. A mechanistic rational accounting for allene racemization and trans-alkene selectivity is discussed.

NAPHTHENIC HYDROCARBON ADDITIVES FOR DIARYL PHOSPHIDE SALT FORMATION

The invention relates to the use of polycyclic aromatic hydrocarbons (PAHs) such as naphthalene and its alkyl, aryl, or heteroatom substituted analogs, that act as catalysts in the presence of an alkali metal (Li, K, Na) for the reduction of electron-deficient and electron-rich triaryl phosphines to their corresponding alkali metal diaryl phosphide salts. The process is also useful for the catalysis of triaryl phosphine chalcogen adducts such as the sulfides, oxides, and selenides, diaryl(halo)phosphines, triaryl phosphine-borane adducts, and tetra-aryl bis(phosphines) that can also be reduced to their corresponding alkali metal diaryl phosphide salts. The invention also relates to small molecule PAHs and polymer tethered PAHs naphthenics.

Method for Producing Polyhydroxyalkanoates

The invention relates to a process for preparing polyhydroxyalkanoates by polymerization of lactones of the general formula I, where the substituents and the index n have the meanings given in the description, in the presence of at least one catalyst of the formula (II) LIMaXam, where the substituents and indices have the meanings given in the description. The invention further relates to poly-3-hydroxybutyrates which have a novel property profile and are obtainable for the first time by means of this process, and also biodegradable polyester mixtures based on these poly-3-hydroxybutyrates.

Hydroformylation process

A process for the production of 4-hydroxybutyraldehyde is described. The process comprises reacting allyl alcohol with a mixture of carbon monoxide and hydrogen in the presence of a solvent and a catalyst system comprising a rhodium complex and a 2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis[bis(3,5-di-n-alkylphenyl)phosphino]butane. The process gives high yield of 4-hydroxybutyraldehyde compared to 3-hydroxy-2-methylpropionaldehyde.

Work-up-free deprotection of borane complexes of phosphines, phosphites, and phosphinites with polymer-supported amines

Borane complexes of phosphorus compounds, a very common oxidation-free relay for catalytic ligands (phosphines, phosphites, and phosphinites), can be easily deprotected by treatment with polymer-supported piperazine or N-methylpiperazine. Deprotection conditions have been optimized for the different types of phosphorus compounds, and the resulting solutions can be used without any intermediate work-up or purification process. Georg Thieme Verlag Stuttgart.

Decarboxylative aldol reactions of allyl β-keto Esters via heterobimetallic catalysis

Mild and selective heterobimetallic-catalyzed decarboxylative aldol reactions involving allyl β-keto esters have been developed. The reaction is promoted by Pd(0)- and Yb(III)-DIOP complexes at room temperature and involves the in situ formation of a ketone enolate from allyl β-keto esters followed by addition of the enolate to aldehydes. The reaction is a new example of heterobimetallic catalysis in which the optimized reaction conditions require the addition of both metals. Copyright

A novel mild deprotection method for phosphine-boranes

Treatment of phosphine-boranes with molecular sieves 4A in a mixture of an ethereal solvent and an alcohol provided deprotected free phosphines in quantitative yields. The phosphines can be obtained by a simple filtration/crystallization procedure in most cases. It should be noted that the current method is successfully applied to the deprotection of a phosphite-borane for the first time.

Process for producing optically active benzhydrol compounds

A process for producing a benzhydrol compound (II) which comprises hydrogenating a benzophenone compound (I) in the presence of a hydrogenation catalyst consisting of a transition metal complex, a base and an optically active diamine compound: STR1 wherein R1 to R10 each represents H, OH, C1-4 alkyl, C1-4 alkoxy, C1-4 alkanoyl, etc., R2 and R3, and R8 and R9 may form --CH=CH--CH=CH--, or any two of R1 to R9 adjacent to each other may be bonded to thereby form --OCH2 O-- or --(CH2)3 --. By using this process, optically active benzhydrol compounds which have a high purity and are useful as, for example, intermediates in the synthesis of drugs can be produced by simple procedures.

Phosphine-borane complexes; Direct use in asymmetric catalysis

An easy and soft method of decomplexation of phosphine-borane complexes, by DABCO, allows its use in situ in asymmetric catalytic hydrogenation of double bonds with metal phosphine complexes.