64896-28-2

Usage

Uses

Used in Catalyst Preparation:
(2S,3S)-(-)-Bis(diphenylphosphino)butane is used as a ligand for the preparation of bimetallic chromium and diphosphine-ruthenium (II) diallyl complexes. Its chiral nature and unique structure contribute to the formation of these complexes, which can be employed in various catalytic processes.
Used in Palladium-Catalyzed Carbon-Carbon Bond Formation:
(2S,3S)-(-)-Bis(diphenylphosphino)butane is used as a ligand in palladium-catalyzed carbon-carbon bond formation reactions. Its presence enhances the selectivity and efficiency of these reactions, leading to the formation of desired products with improved yields.
Used in Pharmaceutical Industry:
(2S,3S)-(-)-Bis(diphenylphosphino)butane is used as a chiral ligand in the synthesis of pharmaceutical compounds. Its ability to influence the selectivity of reactions can be crucial in the production of enantiomerically pure drugs, which is essential for their therapeutic efficacy and safety.
Used in Chemical Research:
(2S,3S)-(-)-Bis(diphenylphosphino)butane is used as a chiral ligand in various research applications, particularly in the field of organometallic chemistry. Its unique properties make it a valuable tool for studying reaction mechanisms, developing new synthetic methods, and exploring the role of chirality in catalysis.

Reaction

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

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

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

Downstream Products

• 113009-11-3 {Mo₂(MeCO₂)2(2S,3S)-bis(diphenylphosphino)butane(MeCN)2}{BF₄}2 
• 94665-46-0 (2S,3S)-(-)-2,3-bis(diphenylphosphinyl)butane 
• 94665-50-6 C₂₈H₅₂P₂ 
• 94665-47-1 C₂₈H₅₂O₂P₂ 
• 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 academic research and scientific papers

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.

Highly Active and Selective Ethylene Oligomerization Catalyst and Method of Preparing Hexene or Octene Using the Same

This invention relates to a chromium complex compound for selective ethylene oligomerization including a chiral ligand, and to a method of selectively preparing 1-hexene or 1-octene from ethylene using the same.

ETHYLENE TETRAMERIZATION CATALYST SYSTEMS AND METHOD FOR PREPARING 1-OCTENE USING THE SAME

Disclosed herein is a method of preparing 1-octene at high activity and high selectivity while stably maintaining reaction activity by tetramerizing ethylene using a chromium-based catalyst system comprising a transition metal or a transition metal precursor, a cocatalyst, and a P—C—C—P backbone structure ligand represented by (R1)(R2)P—(R5)CHCH(R6)—P(R3)(R4).

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.

PREPARATION AND 31P NMR STUDIES OF PLATINUM COMPLEXES OF SOME CHIRAL, BIDENTATE PHOSPHINES

Two chiral diphosphines of formula RN(P(C6H5)2)2, S-peap and S-alap, have been prepared from S-α-phenethylamine and the ethyl ester of S-alanine, respectively.Their syntheses, and the preparation of the achiral diphosphine beap, N,N'-bis(diphenylphosphino)-N,N'-dibenzylethylenediamine, are described.Platinum complexes of these bidentate ligands of formula Pt(chelate)CH3Cl and ClO4 (X=acetone; p-YC5H4N, when Y=CH3, C2H5, CHO, CO2CH3, H and N(CH3)2; and a series of monodentate, Group V donor ligands, P(C2H5)3, P(C3H7)3, P(C8H17)3, PCH3(C6H5)2, P(CH3)2C6H5, P(C6H5)3, P(C6H11)(C6H5)2, P(C6H11)2C6H5, P(C6H11)3, P(C6H5)2N(C2H5)2, As(C6H5)3 and Sb(C6H5)3) have been prepared and their 1H and 31P NMR parameters recorded.The cationic pyridine complexes show a correlation of the ρ values of the para substituent to some of the 31P chemical shifts and coupling constants.The steric and electronic properties of the diphosphine ligands have been investigated by comparing their 31P NMR parameters with those of analogous complexes containing (+)-diop and S,S-chiraphos.