76189-55-4

Basic information

• Product Name: (R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl
• Synonyms: (+)-(1R)-[1,1'-Binaphthalene]-2,2'-diylbis[diphenylphosphine];1,1'-[(1R)-[1,1'-Binaphthalene]-2,2'-diyl]bis[1,1-diphenyl-phosphine;98% (R)-BINAP;(R)-(+)-BINAP, (R)-(+)-1,1'-Binaphthalene-2,2'-diylbis(diphenylphosphane);(R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthalene 97%;(R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl;(R)-(+)-2,2'-Bis(diphenylphosphino)-1;(+/-)-2,2'-Bis(diphenylphosphino)-1,1'-dinaphthalene (BINAP)
• CAS NO: 76189-55-4
• Molecular Formula: C₄₄H₃₂P₂
• Molecular Weight: 622.67
• EINECS: -0
• Product Categories: BINAP Series;Chiral Phosphine;Biphenyl derivatives;chiral;Chiral Reagents;Asymmetric Synthesis;Phosphine Ligands;Synthetic Organic Chemistry;Adamantanes;B (Classes of Boron Compounds);Ligands;N-Heterocyclic Carbene Ligands;Tetrafluoroborates;Peptide;Chiral Compound;Aromatics;Catalyst
• Mol File: 76189-55-4.mol

Chemical Properties

• Melting Point: 283-286 °C(lit.)
• Boiling Point: 724.3 °C at 760 mmHg
• Flash Point: 419 °C
• Appearance: White to cream-white/Powder
• Refractive Index: 235 ° (C=0.3, Toluene)
• Storage Temp.: Room temperature.
• Solubility: Benzene (Slightly), Chloroform (Slightly)
• Water Solubility: insoluble
• Sensitive: Air Sensitive
• Merck: 14,1223
• BRN: 4914063
• CAS DataBase Reference: (R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl(CAS DataBase Reference)
• NIST Chemistry Reference: (R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl(76189-55-4)
• EPA Substance Registry System: (R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl(76189-55-4)

Safety Data

• Hazard Codes: Xi,Xn
• Statements: 36/37/38-20/21/22
• Safety Statements: 22-24/25-37/39-26-36
• WGK Germany: 3
• F: 8-10-23
• TSCA: No
• Hazardous Substances Data: 76189-55-4(Hazardous Substances Data)

Usage

Uses

Used in Metal Mediated Asymmetric Catalysis:
(R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl is used as a chiral ligand for metal-mediated asymmetric catalysis. Its unique chiral structure allows it to selectively bind to metal catalysts, leading to the formation of enantiomerically pure products.
Used in Transition Metal Catalyzed Asymmetric Reactions:
(R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl is a useful ligand for transition metal-catalyzed asymmetric reactions, including hydrogenation and disilylation. Its rhodium and ruthenium derivatives are highly selective homogeneous catalysts used for the reduction of aryl ketones, β-keto esters, and α-amino ketones.
Used in Asymmetric Hydrogenation and Hydroformylation of Olefins:
(R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl and its metal derivatives are employed in asymmetric hydrogenation and hydroformylation of olefins. These reactions are crucial in the synthesis of various pharmaceuticals, agrochemicals, and fine chemicals.
Used in Asymmetric Heck Reactions:
(R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl is used in asymmetric Heck reactions, which are important for the formation of carbon-carbon bonds in organic synthesis. This ligand helps to achieve high enantioselectivity in these reactions.
Used in Asymmetric Isomerizations of Allyls:
(R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl is utilized in asymmetric isomerizations of allyls, which are essential for the synthesis of various chiral compounds.
Used in Asymmetric Aldol Reactions:
Complexes of (R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl with Ag(I) are used to catalyze asymmetric aldol reactions between alkenyl trichloroacetates and aldehydes. This ligand helps to achieve high enantioselectivity in these reactions, which are crucial for the synthesis of various biologically active compounds.
Used in Enantioselective Hetero-Diels-Alder Reactions:
(R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl, in combination with Ag(I), is used to catalyze enantioselective hetero-Diels-Alder reactions of azo compounds. This ligand plays a vital role in achieving high enantioselectivity in these reactions, which are important for the synthesis of complex organic molecules with potential applications in pharmaceuticals and materials science.

Reaction

(R)-BINAP or (R)-Tol-BINAP can be combined with dichloro(1,5-cyclooctadiene)ruthenium to form precursors to NOYORI CATALYST SYSTEMS. These systems exhibit very high catalytic activity and enantioselectivity in the hydrogenation of a wide range of substrates. NOYORI CATALYST SYSTEMS have been shown to effect highly enantioselective hydrogenation of functionalized ketones where the substituents are dialkylamino, hydroxy, siloxy, carbonyl, ester, amide or thioester. Useful ligand in asymmetric Heck processes. Ligand employed in palladium-catalyzed asymmetric arylation of ketones. Ligand employed in rhodium-catalyzed 1,4-additions to enones. Ligand employed in palladium-catalyzed hydroamination of styrene derivatives. Ligand employed in silver-catalyzed asymmetric Sakuri-Hosomi allylation and Mukaiyama aldol reaction. Ligand employed in rhodium-catalyzed kinetic resolution of enynes. Ligand employed in asymmetric rhodium-catalyzed hydroboration of cyclopropenes. Ligand employed in silver-catalyzed a-hydroxylation of stannyl enol ethers. Ligand employed in palladium-catalyzed synthesis of chiral allenes. Ligand for palladium-catalyzed enantioselective hetero Michael addition to form b-amino acid derivatives. Ligand employed in rhodium-catalyzed asymmetric rearrangement of alkynyl alkenyl carbinols. Ligand employed in rhodium-catalyzed 1,2-addition of aluminium organyl compounds to cyclic enones. Ligand employed in iridium-catalyzed transfer hydrogenative allylation of benzylic alcohols. Ligand employed in rhodium-catalyzed asymmetric C-Si bond formation by conjugate silyl transfer using a Si-B linkage. Ligand employed in the iridium-catalyzed asymmetric cyclopropane-mediated carbonyl allylation of primary alcohols. Ligand employed in the nickel-catalyzed asymmetric α-arylation of tetralones. Ligand employed in the copper-catalyzed asymmetric propargylation of ketones. Ligand employed in the cobalt-catalyzed asymmetric reductive coupling of alkynes with alkenes. Ligand employed in the rhodium-catalyzed asymmetric 1,4-addition of arylalanes on trisubstituted enones. Ruthenium-catalyzed asymmetric hydrocyanation of imines. Palladium-catalyzed asymmetric intermolecular cyclization.

Synthetic route

chloro-diphenylphosphine (1079-66-9) + (R)-2,2'-dibromo-1,1'-binaphthyl (86688-08-6) → (R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthalene (76189-55-4)

Conditions	Yield
With n-butyllithium 1.) acetonitrile, -44 deg C, 30 min. 2.) -131 deg C, 30 min.; Yield given. Multistep reaction;

(R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthalene (76189-55-4) → (R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl dioxide

Conditions	Yield
With dihydrogen peroxide In water; acetone	92%

Upstream product

• 74866-28-7 2,2'-dibromo-1,1'-binaphthyl 
• 1079-66-9 chloro-diphenylphosphine 
• 86688-08-6 (R)-2,2'-dibromo-1,1'-binaphthyl 
• 130164-89-5 2,2’-bis(diphenylphosphinooxide)-1,1’-binaphthalene 
• 86632-33-9 (S)-1,1'-binaphthalene-2,2'-diylbis(diphenylphosphine oxide) 
• 128544-05-8 (R)-(-)-1,1'-bi-2-naphthol triflate 
• 829-85-6 diphenylphosphane 
• 126613-06-7 (S)-2,2'-bis((trifluoromethanesulfonyl)oxy)-1,1'-binaphthyl 
• 829-83-4 diphenylarsane 
• 141807-44-5 (+/-)-2,2'-bis(trifluoromethanesulfonyloxy)-1,1-binaphthyl 
• 86632-33-9 (R)-2,2’-bis(1,1-diphenyl-1,1’-phosphine oxide)-1,1’-binaphthyl 
• 4559-70-0 Diphenylphosphine oxide 
• 602-09-5 1,1'-bi-2-naphthol 
• 41593-58-2 diphenylphosphineborane 

Downstream Products

• 137476-81-4 (S)-(+)-1,1'-binaphthyl-2,2'-diylbis<(p-octylbenzyl)diphenylphosphonium> dibromide 
• 204862-91-9 2-(diphenylphosphinyl)-2'-(diphenylphosphanyl)-1,1'-binaphthalene 
• 937-33-7 N-tert-butylaniline 
• 110993-40-3 N-(3,5-dimethylphenyl)-tert-butylamine 
• 740807-00-5 1-(4-Chloro-2-fluoro-5-methoxy-phenyl)-piperazine 
• 303975-55-5 ethyl 4-[4-[4-(7-methoxyheptyloxy)-3,5-dimethylphenyl]piperazin-1-yl]benzoate 
• 303975-65-7 4-[4-(4-phenylpiperidin-1-yl)phenyl]piperazine-1-carboxylic acid tert-butyl ester 
• 303976-10-5 1-[4-[4-(cis-2,6-dimethylmorpholin-4-yl)phenyl]piperazin-1-yl]ethanone 
• 221876-08-0 N-(3-morpholinobenzoyl)morpholine 
• 130164-89-5 2,2’-bis(diphenylphosphinooxide)-1,1’-binaphthalene 
• 625394-33-4 4-(4-chloro-benzenesulfonyl)-6-methyl-8-piperazin-1-yl-3,4-dihydro-2H-benzo[1,4]oxazine 
• 625394-65-2 8-bromo-3,4-dihydro-2H-benzo[1,4]oxazine 
• 192817-79-1 ethyl 2-(morpholin-4-yl)-benzoate 
• 355386-68-4 (R)-N-(1-Aza-bicyclo[2.2.2]oct-3-yl)(5-(3-(4-morpholinyl)phenyl)thiophene-2-carboxamide) 

Relevant articles and documents

The Trityl-Cation Mediated Phosphine Oxides Reduction

Reduction of phosphine oxides into the corresponding phosphines using PhSiH3 as a reducing agent and Ph3C+[B(C6F5)4]? as an initiator is described. The process is highly efficient, reducing a broad range of secondary and tertiary alkyl and arylphosphines, bearing various functional groups in generally good yields. The reaction is believed to proceed through the generation of a silyl cation, which reaction with the phosphine oxide provides a phosphonium salt, further reduced by the silane to afford the desired phosphine along with siloxanes. (Figure presented.).

One-pot synthesis of binaphthyl-based phosphines via direct modification of BINAP

Herein reported is the convenient and efficient strategy for the preparation of binaphthyl-based phosphines through direct modification to the commercially available 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) with sodium. In the absence of 15-crown-5-ether, a cyclic sodium dinapthylphospholide intermediate is mainly generated. With 15-crown-5-ether, P-Ph bonds are selectively cleft by Na to produce binaphthyl-based disodium phosphides. The mechanism of selective formation of sodium dinapthylphospholide or binaphthyl-based disodium phosphides is proposed.

Synthesis method of 2, 2 '-bisdiphenylphosphino-1, 1'-binaphthalene

The invention relates to a synthesis method of 2, 2 '-bisdiphenylphosphino-1, 1'-binaphthalene, which is realized by the following steps: step 1, carrying out BUCHERER reaction on 1, 1 '-binaphthyl-2-naphthol to generate 1, 1'-binaphthyl-2, 2 '-diamine; 2, subjecting 1, 1 '-binaphthyl-2, 2'-diamine to a Sandmeyer reaction to generate binaphthyl dibromide; and 3, carrying out a Grignard reaction onthe binaphthyl dibromide and diphenyl phosphine chloride to generate 2, 2 '-bisdiphenylphosphino-1, 1'-binaphthalene (BINAP). Bulk chemical raw materials are used and are low in price and easy to obtain, and the production cost is effectively reduced; the method has the advantages of easily available raw materials, high reaction yield, simple post-treatment, facilitation of industrial amplification, and strong industrial application prospect.

Synthetic method of 2,2'-double diphenyl phosphine-1,1'-dinaphthalene

The invention discloses a synthetic method of 2,2'-double diphenyl phosphine-1,1'-dinaphthalene. The method comprises the following steps: adding a lithium metal sheet, a ligand, 2,2'-diethoxy-1,1'-dinaphthalene and an ethers solvent are added in a reaction still, heating the materials to the temperature of 60-140 DEG C, reacting the materials for 6-12 hours, dropping chlorodiphenylphosphine at the temperature of 0 DEG C, heating the material to room temperature, and obtaining the product after the reaction is completed; equivalent water quenching is carried out, a product solution is concentrated and filtered, a filter cake is washed with methanol, and vacuum drying is carried out to obtain the product 2,2'-double diphenyl phosphine-1,1'-dinaphthalene (BINAP). The method has the advantages of high yield, low preparation cost, simple post-treatment, high product purity, and is suitable for process enlargement.

Chemoselective Reduction of Phosphine Oxides by 1,3-Diphenyl-Disiloxane

Reduction of phosphine oxides to the corresponding phosphines represents the most straightforward method to prepare these valuable reagents. However, existing methods to reduce phosphine oxides suffer from inadequate chemoselectivity due to the strength of the P=O bond and/or poor atom economy. Herein, we report the discovery of the most powerful chemoselective reductant for this transformation to date, 1,3-diphenyl-disiloxane (DPDS). Additive-free DPDS selectively reduces both secondary and tertiary phosphine oxides with retention of configuration even in the presence of aldehyde, nitro, ester, α,β-unsaturated carbonyls, azocarboxylates, and cyano functional groups. Arrhenius analysis indicates that the activation barrier for reduction by DPDS is significantly lower than any previously calculated silane reduction system. Inclusion of a catalytic Br?nsted acid further reduced the activation barrier and led to the first silane-mediated reduction of acyclic phosphine oxides at room temperature.

Metal-Free Reduction of Phosphine Oxides, Sulfoxides, and N-Oxides with Hydrosilanes using a Borinic Acid Precatalyst

The general reduction of phosphine oxides, sulfoxides, and amine N-oxides was achieved by combining bis(2-chlorophenyl)borinic acid with phenylsilane. The reaction was shown to tolerate a wide range of substrates and could be performed under mild conditions, with only 2.5 mol % of the easily synthesized catalyst. Mechanistic investigations pointed to a key borohydride as the real catalyst and at bis(2-chlorophenyl)borinic acid as a precatalyst.

Highly efficient reduction of tertiary phosphine oxides and sulfides with amine-assisted aluminum hydrides under mild conditions

Reduction of tertiary phosphine oxides and sulfides into the corresponding phosphines with amine-assisted aluminum hydrides has been studied. The method is characterized by mild conditions, short reaction time, high efficiency, and expanded substrate scope. The new method is an alternative to the currently used methods of reducing phosphine oxides or recycling phosphines engaged in organic reactions.

Improved syntheses of phosphine ligands by direct coupling of diarylbromophosphine with organometallic reagents

Br versus Cl: It is found that the use of diarylbromophosphines instead of diarylchlorophosphines is crucial for their direct coupling with binaphthylmagnesium bromide or BINOL triflate. This finding has led to an improved preparation of both electron-deficient BINAP-type phosphine ligands and several important Buchwald's ligands. Copyright

Process research on the asymmetric hydrogenation of a benzophenone for developing the manufacturing process of the squalene synthase inhibitor TAK-475

A practical synthetic method for the synthesis of the chiral benzhydrol 8, which is the key intermediate of the squalene synthase inhibitor TAK-475 (1), has been developed. The method, via asymmetric hydrogenation of the benzophenone 7, employed Noyori's ruthenium precatalyst of the type [RuCl 2(diphosphine)(diamine). We focused on tuning of the chiral diphosphine, and have discovered a novel ligand, DADMP-BINAP (18c), for the catalyst that has allowed reduction of the operating pressure in the asymmetric hydrogenation. The precatalyst containing 18c performed effectively at low hydrogen pressure (1 MPa) with sufficient enantioselectivity, and the result enabled us to successfully obtain enantiomerically pure 8 on a multikilogram scale.

BINAP versus BINAP(O) in asymmetric intermolecular Mizoroki-Heck reactions: Substantial effects on selectivities

2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) was employed as chiral ligand in the enantioselective intermolecular Mizoroki-Heck reaction, whereas the use of cognate BINAP(O) (monooxidized BINAP) is unprecedented. The regio- and enantioselectivity of the arylation of representative cyclic alkenes changes dramatically in the presence of hemilabile BINAP(O) instead of BINAP. The arylation of 2,3-dihydrofuran is perfectly regiodivergent (98:2 versus 0:100) and the arylation of cyclopentene is only enantioselective with BINAP(O) [60 versus 10% enantiomeric excess (ee)]. Use of [Pd2(dba)3]·dba (dba=dibenzylideneacetone) instead of Pd(OAc)2 produces as high as 86% ee in the arylation of cyclopentene.