Preparation and Enantiomeric Excess Determination of Optically Active BINOL and BINOL Derivatives

Love, Brian E.

doi:10.2174/157017906776819178

Cited by 14 publications

(3 citation statements)

References 85 publications

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“…[13] Another aspect is that binaphthyl compounds are usually prepared as racemic mixtures, which must be subsequently resolved into the enantiomers. [14,15] Modern strategies aim at direct synthesis of pure binaphthyl enantiomers. [16][17][18][19][20][21][22] For an efficient design of novel coupling catalysts, [23] a profound mechanistic understanding of the reaction sequence is of huge advantage.…”

Section: Introductionmentioning

confidence: 99%

Gas‐Phase Study on the CC Coupling of Naphthol Catalyzed by Cu^II⋅TMEDA: Evidence for the Key Role of Binuclear Clusters

Roithová

Schröder

2008

Chemistry A European J

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The mechanism of oxidative coupling of two naphthol molecules to form binaphthol catalyzed by Cu(OH)ClTMEDA (TMEDA=N,N,N',N'-tetramethylethylenediamine) was approached by means of a gas-phase model system. Concise evidence is provided that the coupling reaction proceeds in clusters with two Cu(II) centers, whereby the intermediacy of free naphthoxy radicals in the coupling step is avoided. In the absence of TMEDA, the cluster is bound via a bridging counterion and the coupling reaction is followed by cluster cleavage. The coordination of one or two TMEDA molecules to the reactive complex results in more efficient coupling of naphthol molecules, and moreover, the binuclear cluster is also conserved after the reaction is completed. The effect of TMEDA is twofold: First, it supports clustering of copper and, second, as a ligand bound to a copper center in the reactive complex, it weakens the bond between copper and the naphtholato ligand such that the naphtholato unit is more prone to undergo C--C coupling. Furthermore, a pronounced counterion effect is found that correlates well with condensed-phase data: weakly bridging counterions (e.g., NO3(-)) yield less stable dicopper clusters and the coupling reaction hardly occurs, whereas better bridging counterions (e.g., Cl(-) or Br(-)) provide more stable clusters that make the coupling reaction more efficient.

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Section: Introductionmentioning

confidence: 99%

Gas‐Phase Study on the CC Coupling of Naphthol Catalyzed by Cu^II⋅TMEDA: Evidence for the Key Role of Binuclear Clusters

Roithová

Schröder

2008

Chemistry A European J

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“…The synthesis of enantiomerically pure ( R )- or ( S )-BINOL 1 has been extensively studied, and two major different approaches have been developed: enzymatic or chemical resolution of racemic BINOL 1 and direct stoichiometric or catalytic oxidative coupling synthesis …”

Section: 2 Preparation Of (R) and (S)-binolmentioning

confidence: 99%

Update 1 of: BINOL: A Versatile Chiral Reagent

Brunel¹

2007

Chem. Rev.

228

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“…8,10–12 Accessing enantiopure Binol has substantial economic and scientific interest. 13–15 In 1993, Hirata et al resolved Binol by cocrystallization with enantiopure N , N ′-dimethyl-1,2-diphenylethane-1,2-diamine (DADPE). 8 They suspected the existence of a ( R )-Binol-( R , R )-DADPE cocrystal phase (( R )-( R , R )) (Scheme 1).…”

mentioning

confidence: 99%

Using the nature of the achiral solvent to orient chiral resolution

de Meester,

Shemchuk,

Collard

et al. 2024

CrystEngComm

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Preparation and Enantiomeric Excess Determination of Optically Active BINOL and BINOL Derivatives

Cited by 14 publications

References 85 publications

Gas‐Phase Study on the CC Coupling of Naphthol Catalyzed by Cu^II⋅TMEDA: Evidence for the Key Role of Binuclear Clusters

Gas‐Phase Study on the CC Coupling of Naphthol Catalyzed by Cu^II⋅TMEDA: Evidence for the Key Role of Binuclear Clusters

Update 1 of: BINOL: A Versatile Chiral Reagent

Using the nature of the achiral solvent to orient chiral resolution

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Preparation and Enantiomeric Excess Determination of Optically Active BINOL and BINOL Derivatives

Cited by 14 publications

References 85 publications

Gas‐Phase Study on the CC Coupling of Naphthol Catalyzed by CuII⋅TMEDA: Evidence for the Key Role of Binuclear Clusters

Gas‐Phase Study on the CC Coupling of Naphthol Catalyzed by CuII⋅TMEDA: Evidence for the Key Role of Binuclear Clusters

Update 1 of: BINOL: A Versatile Chiral Reagent

Using the nature of the achiral solvent to orient chiral resolution

Contact Info

Product

Resources

About

Gas‐Phase Study on the CC Coupling of Naphthol Catalyzed by Cu^II⋅TMEDA: Evidence for the Key Role of Binuclear Clusters

Gas‐Phase Study on the CC Coupling of Naphthol Catalyzed by Cu^II⋅TMEDA: Evidence for the Key Role of Binuclear Clusters