Binaphthalenes

Amino-l-naphthalenecarboxyhc acid can be converted, by dia2oti2ation and treatment with ammoniacal cuprous oxide, to l,l -binaphthalene-8,8 -dicarboxyhc acid [29878-91-9] (48). Treatment of (48) with concentrated sulfuric acid yields anthranthrone. The dihalogenated anthranthrones are valuable vat dyes. 

Atropoisomeric binaphthalene-core phosphacyclic derivatives in coordination chemistry and homogeneous catalysis 97CB543. 

Nakagawa and coworkers reported a chiral ytterbium catalyst 34 which was prepared from l,l -(2,2 -bisacylamino)binaphthalene and Yb(OTf)3 in the presence of diisopro-pylethylamine by a method similar to that used for Kobayashi s chiral ytterbium reagent [52] (Scheme 1.65, Table 1.66). The amine also plays an important role in this reaction, because racemic cycloadducts were obtained without the tert-amine. Reduc-... 

In an oven dried glass flask under an argon atmosphere at — 78 UC, 950 mg (5 mmol) of methyl 2,3-dihydro-1-oxo-l/f-indene-2-carboxylate in 10 mL of toluene are added to 2.2 mg (0.2 mmol) of potassium rert-butoxide in 5 mL of toluene. 356 mg (0.2 mmol) of (5, 6 )-bis[3,3 -dimethyl-l,l -binaphthalene]-2,2 -diol bis(diethy-lencoxy) ether [(5,.5)-3) are added, followed after 10 min by 700 mg (10 mmol) of 3-buten-2-one in 10 mL of toluene and the mixture is stirred for 120 h at — 78 °C after which it is poured into 35 mL of sat. aq NH4C1. The toluene layer combined with a toluene wash solution is dried over MgS04 and evaporated at 40 "C. The crude adduct is purified by chromatography over silica gel (C H2C12) yield 624 mg (48%) 99% ee. 

Various chiral crown ethers based on [1,1 -binaphthalene]-2.2 -diol, lactose or other chiral 1,2-di-ols were tested as catalyst in the addition of methyl benzcneacetate to methyl 2-propenoate using sodium amide or potassium tert-butoxide as the base. Some pertinent examples are given261 262 396. 

In general the chiral additive (l/ ,2/J)-l,2-dimethoxy-l,2-diphenylethane was the most effective while (.S )-2.2 -diniethoxy-1,1 -binaphthalene and (1 / ,27 )-/V,/V,/V, A"-tetramethyl-1,2-diphcnyl-ethylenediamine induced only very low levels of enantiofacial differentiation. In the case of the acyclic enimines competing 1,2-addition products were also obtained7. 

Tetrahydro-l,l -binaphthalene (bisdialine) (85) is more reactive than the corresponding 1,1 -binaphthalene and has been used as a 47t component of cycloadditions to prepare very complex molecules. An improved method for preparing 85 was recently described [90]. The Diels Alder reactions of 85 with a number of dienophiles were studied [90, 91] and are illustrated in Scheme 2.38. 

In recent years, axially chiral binaphthalene derivatives have emerged as important ligands and chiraUty inducers in organic synthesis. Oxidative coupling of 2-naphthols represents a well estabhshed method for the preparation of binaphthols. The couplings are usually carried out by treating naphthols with more than an equimolar amount of a metal such as Fe(III), Mn(III),... 

Zeijden [112] used chiral M-functionalized cyclopentadiene ligands to prepare a series of transition metal complexes. The zirconium derivative (82 in Scheme 46), as a moderate Lewis acid, catalyzed the Diels-Alder reaction between methacroleine and cyclopentadiene, with 72% de but no measurable enantiomeric excess. Nakagawa [113] reported l,T-(2,2 -bis-acylamino)binaphthalene (83 in Scheme 46) to be effective in the ytterbium-catalyzed asymmetric Diels-Alder reaction between cyclopentadiene and crotonyl-l,3-oxazolidin-2-one. The adduct was obtained with high yield and enantioselectivity (97% yield, endo/exo = 91/9, > 98% ee for the endo adduct). The addition of diisopropylethylamine was necessary to afford high enantioselectivities, since without this additive, the product was essentially... 

In 2004, Shi et al. reported Pd-catalysed asymmetric allylic substitutions using axially chiral S/S- and S/O-heterodonor ligands based on the binaphthalene backbone. The test reaction was performed in the presence of... 

Scheme 1.9 Test reaction with S/S- and S/O-heterodonor ligands with binaphthalene backbone.

The preparation of BINAP reported in 1980 has marked a landmark in asymmetric catalysis and has illustrated the peculiar stereorecognitive properties inherent with the axially chiral 1,1 -binaphthalene framework. Since then, a great deal of work has been devoted to the preparation of binaphthalene-templated ligands of related design. These efforts have resulted in the... 

Scheme 1.28 Test reaction with binaphthalene-templated S/N ligand with achiral oxazoline pendant.

Scheme 2.2 Cu-catalysed 1,4-additions of ZnEt2 and AlMe3 to ( )-3-nonen-2-one with 1,1 -binaphthalene-derived ligands.

AIMcs to cyclohexadienone with thioether hgands 86-7 AlMes to linear aliphahc enones with binaphthalene-derived hgands 75-8... 

A chiral zirconium catalyst generated from Zr(0,-Bu)4 and (R)-3,3 -diiodo-1,1 -binaphthalene-2,2 -diol [(f )-3,3/-l2BINOL] catalyzed... 

Using cationic [Rh(cod)2]2 SbF6 and (S)-BINAP (BINAP = 2,2 -bis(di-phenylphosphino)-l,T-binaphthalene) as the chiral hgand, the substrates 129 can be reductively coupled using HBCat (Cat = 1,2-benzenediolate) as the... 

In determination of the absolute configuration of a-chiral primary amines, BINOL derivatives were used as chiral derivatizing agent.10 In this procedure, the chiral substrate was derivatized with R and S enantiomers of the 2,-methoxy-l,l -binaphthalene-8-carbaldehyde and the XH spectra of both diastereomers were compared. Comparison of the chemical shift differences of the diastereomers has allowed determination of the absolute configuration of the chiral substrate [5]. 

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