64896-28-2

Basic information

• Product Name: (2S,3S)-(-)-BIS(DIPHENYLPHOSPHINO)BUTANE
• Synonyms: (2S,3S)-(-)-BIS(DIPHENYLPHOSPHINO)BUTANE;(2S,3S)-(-)-2,3-BIS(DIPHENYLPHOSPHINO)BUTANE;(S,S)-CHIRAPHOS;(2S,3S)-(-)-Bis(diphenylphosphino)butane,(S,S)-CHIRAPHOS;(2S 3S)-(-)-2 3-BIS(DIPHENYLPHOSPHINO)-&;(2S,3S)-(-)-BIS(DIPHENYLPHOSPHINO)BUTANE (S,S)-CHIRAPHOS, (C=1.5,CHCL3);SULFONYLCHLORIDE,SULFURICOXY,SULFURYLCHLORIDE,CHLOROSLFURICACID,SULFURICCHLORIDE/(S,S)-CHIRAPHOS;(S,S)-Chiraphos, (2S,3S)-(-)-2,3-Bis(diphenylphosphino)butane
• CAS NO: 64896-28-2
• Molecular Formula: C₂₈H₂₈P₂
• Molecular Weight: 426.47
• Product Categories: Asymmetric Synthesis;Phosphine Ligands;Synthetic Organic Chemistry;organophosphine ligand;Chiral Phosphine
• Mol File: 64896-28-2.mol
• Article Data: 6

Chemical Properties

• Melting Point: 104-109 °C
• Boiling Point: 529.19 °C at 760 mmHg
• Flash Point: 291.15 °C
• Appearance: white/crystal
• Vapor Pressure: 0mmHg at 25°C
• Storage Temp.: under inert gas (nitrogen or Argon) at 2-8°C
• Solubility: Acetonitrile, Chloroform
• Sensitive: Air Sensitive
• Merck: 14,2063
• BRN: 4268869
• CAS DataBase Reference: (2S,3S)-(-)-BIS(DIPHENYLPHOSPHINO)BUTANE(CAS DataBase Reference)
• NIST Chemistry Reference: (2S,3S)-(-)-BIS(DIPHENYLPHOSPHINO)BUTANE(64896-28-2)
• EPA Substance Registry System: (2S,3S)-(-)-BIS(DIPHENYLPHOSPHINO)BUTANE(64896-28-2)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 37/39-26-36
• WGK Germany: 3
• TSCA: No
• Hazardous Substances Data: 64896-28-2(Hazardous Substances Data)

Usage

Uses

Different sources of media describe the Uses of 64896-28-2 differently. You can refer to the following data:
1. (2S,3S)-(-)-Bis(diphenylphosphino)butane, also known as (S,S)-Chiraphos, is a chiral ligand used in the preparation of bimetallic chromium and diphosphine-ruthenium (II) diallyl complexes.
2. Ligand for palladium-catalyzed carbon-carbon bond formation.
3. Ligand for Pd-catalyzed carbon-carbon bond formation.

Reaction

Useful as a ligand in the Ni-catalyzed asymmetric additions to allylic ketals.

Chemical Properties

white granular powder

InChI:InChI=1/C28H28P2/c1-23(29(25-15-7-3-8-16-25)26-17-9-4-10-18-26)24(2)30(27-19-11-5-12-20-27)28-21-13-6-14-22-28/h3-24H,1-2H3/t23-,24-/m0/s1

Synthetic route

(3S,4S,5R)-3,4-Bis-diphenylphosphanyl-5-((1R,2S,5R)-2-isopropyl-5-methyl-cyclohexyloxy)-dihydro-furan-2-one → (2S,3S)-2,3-bis(diphenylphosphino)butane (64896-28-2)

Conditions	Yield
Yield given. Multistep reaction;

triphenylphosphine (603-35-0) + (2R,3R)-butane-2,3-diyl dimethanesulfonate (81495-76-3) → (2S,3S)-2,3-bis(diphenylphosphino)butane (64896-28-2)

Conditions	Yield
With sodium cyanide; tertiary butyl chloride; sodium thiocyanide; lithium; nickel(II) nitrate Yield given. Multistep reaction;

chloro-diphenylphosphine (1079-66-9) → (2S,3S)-2,3-bis(diphenylphosphino)butane (64896-28-2)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1.) THF, hexane, -90 deg C, 1.5 h, 2. a) from -90 deg C to RT, 3 h, b) RT, 16 h View Scheme

lithium diphenylphosphide (65567-06-8, 4541-02-0) → (2S,3S)-2,3-bis(diphenylphosphino)butane (64896-28-2)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1.) THF, hexane, -90 deg C, 1.5 h, 2. a) from -90 deg C to RT, 3 h, b) RT, 16 h View Scheme

-2,3-butandiol di-(4-methylbenzolsulfonat) (64896-27-1) + lithium diphenylphosphide (65567-06-8, 4541-02-0) → (2S,3S)-2,3-bis(diphenylphosphino)butane (64896-28-2)

Conditions	Yield
In tetrahydrofuran at -4 - 20℃;
Stage #1: -2,3-butandiol di-(4-methylbenzolsulfonat); lithium diphenylphosphide With nickel(II) perchlorate hexahydrate In tetrahydrofuran Inert atmosphere; Stage #2: With sodium thiocyanate In ethanol Inert atmosphere; Stage #3: With sodium cyanide In ethanol Inert atmosphere;

[Ni((S,S)-chiraphos)2NCS]NCS → (2S,3S)-2,3-bis(diphenylphosphino)butane (64896-28-2)

Conditions	Yield
With sodium cyanide In ethanol; water Inert atmosphere;
With sodium cyanide In ethanol; water Inert atmosphere; Heating;

C28H34B2P2 → (2S,3S)-2,3-bis(diphenylphosphino)butane (64896-28-2)

Conditions	Yield
With 1,4-diaza-bicyclo[2.2.2]octane In toluene at 110℃; for 1h; Inert atmosphere;

diphenylphosphineborane (41593-58-2) → (2S,3S)-2,3-bis(diphenylphosphino)butane (64896-28-2)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: tert-butylmagnesium chloride / tetrahydrofuran / 1 h / 20 °C / Inert atmosphere; Sonication 1.2: 20 h / 20 °C / Inert atmosphere 2.1: 1,4-diaza-bicyclo[2.2.2]octane / toluene / 1 h / 110 °C / Inert atmosphere View Scheme
Multi-step reaction with 2 steps 1.1: tert-butylmagnesium chloride / tetrahydrofuran / 1 h / 20 °C / Inert atmosphere; Sonication 1.2: 20 h / 20 °C / Inert atmosphere 2.1: 1,4-diaza-bicyclo[2.2.2]octane / toluene / 1 h / 110 °C / Inert atmosphere View Scheme
Multi-step reaction with 2 steps 1.1: tert-butylmagnesium chloride / tetrahydrofuran / 1 h / 20 °C / Inert atmosphere; Sonication 1.2: 20 h / 20 °C / Inert atmosphere 2.1: 1,4-diaza-bicyclo[2.2.2]octane / toluene / 1 h / 110 °C / Inert atmosphere View Scheme
Multi-step reaction with 2 steps 1.1: allylmagnesium bromide / tetrahydrofuran / 1 h / 20 °C / Inert atmosphere 1.2: 20 h / 20 °C / Inert atmosphere; Sonication 2.1: 1,4-diaza-bicyclo[2.2.2]octane / toluene / 1 h / 110 °C / Inert atmosphere View Scheme
Multi-step reaction with 2 steps 1.1: lithium hexamethyldisilazane / tetrahydrofuran / 1 h / 20 °C / Inert atmosphere 1.2: 20 h / 20 °C / Inert atmosphere 2.1: 1,4-diaza-bicyclo[2.2.2]octane / toluene / 1 h / 110 °C / Inert atmosphere View Scheme

tris(dibenzylideneacetone)dipalladium (0) + [10-bromo-5,15-diphenylporphyrinato]-magnesium(II) (193265-35-9) + (2S,3S)-2,3-bis(diphenylphosphino)butane (64896-28-2) → [PdBr(10,20-diphenylporphyrinatonickel(II))((S,S)-2,3-bis(diphenylphosphino)butane)]

Conditions	Yield
In toluene (Ar); Schlenk technique; P ligand was added to hot (105°C) toluene; Pd compd. was added; stirred for 5 min; Ni complex was added; stirredat 105°C for 2 h; TLC monitoring; cooled to room temp.; concd. (vac.); hexane added; filtered; washed (hexane); dried (vac.); elem. anal.;	99%

(Pd((CH3)2NC2H4N(CH3)2)(CH3C6H4CHN(CH2C6H5)COC7H7))(1+)*CF3SO3(1-)=(Pd((CH3)2NC2H4N(CH3)2)(C7H7CHN(C7H7)COC7H7))CF3SO3 (1116524-79-8) + (2S,3S)-2,3-bis(diphenylphosphino)butane (64896-28-2) → (Pd(((C6H5)2PCHCH3)2)(CH3C6H4CHN(CH2C6H5)COCH2C6H5))(1+)*CF3SO3(1-)=(Pd(((C6H5)2PCHCH3)2)(CH3C6H4CHN(C7H7)COC7H7))CF3SO3

Conditions	Yield
In dichloromethane under Ar atm. soln. Pd complex and (2S,3S)-bis(diphenylphosphino)butane in CH2Cl2 was stirred for 3.5 h at r.t.; solvent was removed in vacuo, flash chromy. on silica (CH2Cl2-MeOH 19:1); elem. anal.;	99%

[bis(μ-chloro[(R)-N,N-dimethyl(α-methylbenzyl)amino-2-C,N]palladium(II))] + silver trifluoromethanesulfonate (2923-28-6) + (2S,3S)-2,3-bis(diphenylphosphino)butane (64896-28-2) → [((R)-(+)-N,N-dimethyl-1-phenylethylamine-N,C)Pd((2S,3S)-2,3-bis(diphenylphosphino)butane)][CF3SO3]

Conditions	Yield
In dichloromethane (N2) to 1 equiv of Pd-complex were added 2 equiv of diphosphine and 2 equiv of CF3SO3Ag in CH2Cl2, the mixt. was stirred at 25°C for 3 h; sepd., reduced in vac.; elem. anal.;	98%

methylidenetricobalt nonacarbonyl (15664-75-2) + (2S,3S)-2,3-bis(diphenylphosphino)butane (64896-28-2) → [Co3(μ3-CH)(CO)7((2S,3S)-(-)-bis(diphenylphosphino)butane)]

Conditions	Yield
In hexane under Ar or N2; a soln. of Co-contg. compd. (22.6E-6 mol) and a ligand (23.5E-6 mol) was heated slowly to reflux under stirring; monitoring by spot TLC (eluent: hexane-CH2Cl2 (2:1 v/v)); the compd. wasconcd. and dried under vac.;	98%

trans-bis(triphenylphosphino)Pt(CF3)Cl (71581-10-7) + (2S,3S)-2,3-bis(diphenylphosphino)butane (64896-28-2) → (chiraphos)Pt(CF3)Cl

Conditions	Yield
In toluene suspn. of Pt-complex and chiraphos was stirred for 24 h at room temp. under N2 (Schlenk flask); concd., Et2O added, ppt. was filtered off, washed with Et2O, recrystd. from CH2Cl2-Et2O; elem. anal.;	96%

trans-[(Pt(PPh2)2)2(3,5-(CCC(CPh2)CC)2-C5H3N)2] + (2S,3S)-2,3-bis(diphenylphosphino)butane (64896-28-2) → cis-[Pt(S,S-chiraphos)(3,5-(CCC(CPh2)CC)2-C5H3N)2Pt(S,S-chiraphos)]

Conditions	Yield
In dichloromethane at room temp. for 14 h;	96%

Pt(N,N′-dicyclohexylimidazol-2-ylidene)(divinyltetramethylsiloxane) + iodine (7553-56-2) + (2S,3S)-2,3-bis(diphenylphosphino)butane (64896-28-2) → (N,N'-dicyclohexylimidazolylidene)Pt((S,S)-Chiraphos)I2

Conditions	Yield
In toluene under Ar atm. soln. I2 in toluene was added at 0°C to soln. Pt complex in toluene, soln. ligand in toluene was added at 0°C and stirred at room temp. overnight;	96%

chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium (II) (32993-05-8) + hexane (110-54-3) + (2S,3S)-2,3-bis(diphenylphosphino)butane (64896-28-2) + toluene (108-88-3) → [Ru(C5H5)Cl((C6H5)2PCH(CH3)CH(CH3)P(C6H5)2)]*0.3C6H14*0.3C7H8

Conditions	Yield
In toluene byproducts: PPh3; (Ar); std. Schlenk technique; soln. of Ru complex and ligand in toluene was stirred at 90°C for 16 h; cooled to room temp.; chromd. (silica gel, toluene, EtOAc); concd. (vac.); petroleum ether added; elem. anal.;	96%

tris(propionitrile)tricarbonylmolybdenum(0) (103933-26-2) + (2S,3S)-2,3-bis(diphenylphosphino)butane (64896-28-2) → (Mo(CO)3(2(S),3(S)-bis(diphenylphosphino)butane)(NCEt))

Conditions	Yield
In further solvent(s) (Mo(CO)3(NCEt)3) and chir were suspender in propionitrile, immersed for 5 min into ultrasonic bath and stirred for 1 h at 20°C; Et2O was added, ppt. was filtered off, washed with Et2O and dried under vac.; elem. anal.;	95%

[(η5-C5H4COCH3)(PPh3)2RuCl] + (2S,3S)-2,3-bis(diphenylphosphino)butane (64896-28-2) → [(η5-C5H4COCH3)((2S,3S)-(-)-Ph2PCMeCHMePPh2)RuCl]

Conditions	Yield
In benzene thermal reaction, C6H6, 4 h (N2); recrystd. from n-hexane-CH2Cl2; elem. anal.;	95%

ammonium hexafluorophosphate + bis(methanol)-tetra-μ-benzoato(O,O')-diruthenium(II,III) hexafluorophosphate + (2S,3S)-2,3-bis(diphenylphosphino)butane (64896-28-2) → Δ-(benzoato-O,O′)-bis(S,S-1,2-bis(diphenylphosphino)butane-P,P')ruthenium(II) hexafluorophosphate

Conditions	Yield
Stage #1: bis(methanol)-tetra-μ-benzoato(O,O')-diruthenium(II,III) hexafluorophosphate; (2S,3S)-2,3-bis(diphenylphosphino)butane In methanol for 12h; Inert atmosphere; Reflux; Stage #2: ammonium hexafluorophosphate at -10℃; Inert atmosphere; diastereoselective reaction;	95%

dichloro(1,5-cyclooctadiene)platinum(ll) (12080-32-9) + (2S,3S)-2,3-bis(diphenylphosphino)butane (64896-28-2) → PtCl2((2S,3S)-2,3-bis(diphenylphosphino)butane)(II)

Conditions	Yield
In dichloromethane dissolving of Pt-complex and S,S-chiraphos in CH2Cl2, stirring for 30 min; addn. of MeOH, evapn. of CH2Cl2 under vac., elem. anal.;	94%
In dichloromethane N2-atmosphere; 20°C;

Upstream product

• 64896-27-1 -2,3-butandiol di-(4-methylbenzolsulfonat) 
• 65567-06-8 lithium diphenylphosphide 
• 41593-58-2 diphenylphosphineborane 
• 1079-66-9 chloro-diphenylphosphine 
• 603-35-0 triphenylphosphine 
• 81495-76-3 (R,R)-2,3-butanediol bis(methanesulfonate) 

Downstream Products

• 91871-18-0 ((C₆H₅)2PCH(CH₃)CH(CH₃)P(C₆H₅)2)(NiCH(CH₃)CH₂COO) 
• 91926-62-4 ((C₆H₅)2PCH(CH₃)CH(CH₃)P(C₆H₅)2)(NiCH(CH₃)CH₂COO) 
• 91871-17-9 ((C₆H₅)2PCH(CH₃)CH(CH₃)P(C₆H₅)2)NiCH₂CH(CH₃)COO 

Relevant articles and documents

Synthesis of novel C2 and C1 symmetric chiraphos derivatives and their application in palladium-catalyzed miyauramichael reaction

A new method for the synthesis of C2 and C1 symmetric CHIRAPHOS derivatives and their application in Pd-catalyzed 1,4-addition reaction of an aryl boron compound to an ,￠-unsaturated carbonyl compound (MiyauraMichael reaction) are described. Six CHIRAPHOS congeners are prepared by substitution reactions of (2R,3R)-butane-2,3-diyl ditosylate with metalated phosphineborane adducts and subsequent deprotection of the resulting borane-protected bisphosphines. In the asymmetric MiyauraMichael reaction, the CHIRAPHOS derivative containing 4-tolyl groups showed a higher enantioselectivity than the others including parent CHIRAPHOS.

Ethylene oligomerization catalyst systems having enhanced selectivity

Disclosed herein is a catalyst system for selective oligomerization of ethylene, which comprises a P—C—C—P frame-work ligand, which is (R1)(R2)P—(R5)CHCH(R6)—P(R3)(R4), and a chromium-based metal compound. Also disclosed is a method of greatly enhancing the activity and selectivity of oligomerization, such as trimerization or tetramerization, using a ligand having a specific steric arrangement structure.

Michael Addition of Lithiodiphenylphosphine to Menthyloxy-2-Furanone: Enantioselective Synthesis of S,S-CHIRAPHOS

The preparation of enantiomerically pure (2S,3S)-2,3-bis(diphenylphosphino)butane (S,S-CHIRAPHOS) in 35percent overall yield from readily available γ-menthoxybutenolide is described.