1.1'-Binaphthyl-2.2'-diphemyl phosphine

Description

The two BINAP enantiomers [(S)-BINAP is shown] are widely used as ligands in enantioselective organic synthesis. BINAP has no specific stereogenic centers; its chirality stems from sterically restricted rotation about the bond that connects the naphthalene rings. The 2001 Nobel Prize in Chemistry was awarded to Ryoji Noyori in part for his group’s development of this technology.

Description

rac-BINAP is a racemic mixture of (R)-BINAP and (S)-BINAP. rac-BINAP is commonly used as a bidentate phosphine ligand in palladium catalyzed cross-coupling reactions.

Chemical properties

1.1'-Binaphthyl-2.2'-diphemyl phosphine is White to light beige powder

The Uses of 1.1'-Binaphthyl-2.2'-diphemyl phosphine

1. racemic-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl ( (+/-)-BINAP ) is an essential role in the organic synthesis of enantioselective transformations catalyzed by the complexes of ruthenium, rhodium and palladium.
2. It is also employed in palladium-catalyzed arylamine coupling in the preparation of demethylthiocholchines.
3. used with Cu(II) to catalyze the addition of arylsulfonamides to styrenes and olefins.

The Uses of 1.1'-Binaphthyl-2.2'-diphemyl phosphine

A mixture of the chloride (25 g, 168 mmol), the amine (40 g, 168 mmol), Pd(OAc)2 (1.5 g, 6.72 mmol), (+-) BINAP (4.18 g, 6.72 mmol), and Cs2CO3 (76.7 g, 235.2 mmol) in toluene (800 mL) was stirred at 90 C under N2 for 23 h. The mixture was filtered through a pad of celite and washed with EtOAc. The filtrate was concentrated in vacuo and purified by silica gel flash chromatography (1:5 EtOAc/petroleum ether) to provide the product as a red solid. [22.4 g, 37%]

The Uses of 1.1'-Binaphthyl-2.2'-diphemyl phosphine

(^+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl plays an essential role in the organic synthesis of enantioselective transformations catalyzed by the complexes of ruthenium, rhodium and palladium. It is also employed in palladium-catalyzed arylamine coupling in the preparation of demethylthiocholchines. It is used with Cu(II) to catalyze the addition of arylsulfonamides to styrenes and olefins.

The Uses of 1.1'-Binaphthyl-2.2'-diphemyl phosphine

2,2'-Bis(diphenylphosphino)-1,1'-dinaphthalene is a powerful chiral auxiliary that is used as a homogeneous catalyst in some asymmetric chemical syntheses. 2,2'-Bis(diphenylphosphino)-1,1'-dinaphthalene is utilized for its high enantioselectivity and is used as a ligand to create coordination complexes.

Reactions

Phosphine Ligand Kit component.

1. Useful ligand for palladium-catalyzed carbon-nitrogen bond formation.
2. Useful ligand for rhodium-catalyzed C-C bond formation.
3. Useful ligand for palladium-catalyzed intramolecular acylation of aryl bromides via C-H activation.
4. Used in the preparation of Buchwald third generation precatalyst.
5. Used in methoxy directed Rhodium migration.
6. Used in Nickel catalyzed C-N cross-coupling reactions.
   

General Description

Racemic version of BINAP.

Purification Methods

Dissolve the enantiomer in toluene, wash it with 30% aqueous NaOH, three times with H2O, dry (Na2SO4), evaporate to ~15% of its volume and add an equal volume of degassed MeOH. Collect the solid, wash it with MeOH and dry it at 80o/0.005mm for 6hours. Recrystallise it from a 1:1 mixture of toluene/EtOH to optical purity (m 241-242o) [Takaya et al. Org Synth 67 20 1989]. [Noyori & Takaya Acc Chem Res 2 3 345 1990, Kitamura et al. Org Synth 71 1 1993, Takaya et al. Org Synth 72 74 1995, Kitamura et al. J Org Chem 57 4053 1992.]