Enantioselective Synthesis of Binaphthol Derivatives by Oxidative Coupling of Naphthol Derivatives Catalyzed by Chiral Diamine·Copper Complexes

Nakajima, Makoto; Miyoshi, Irie; Kanayama, Kumiko; Hashimoto, Seiya; Noji, Masahiro; Koga, Kenji

doi:10.1021/jo981808t

Cited by 315 publications

(138 citation statements)

References 28 publications

Supporting

Mentioning

133

Contrasting

Unclassified

Order By: Relevance

“…These observations suggest that the presence of chelating substituents and less hindered catalysts enables the substrate to remain bound to chiral catalyst till the coupling reaction is completed (Scheme 4). Similar observation has been reported in chiral amine -copper complex catalyzed reactions [24].…”

Section: Stereoselectivity Of Biaryl Couplingsupporting

confidence: 90%

“…Enantioselective oxidative coupling of 2-naphthol is an important oxidation reaction in asymmetric synthesis [20][21][22]. Enantioselective oxidative coupling of 2-naphthol using chiral copper amine complexes has been attempted by several research groups [23][24][25]. Moreover copper N,N,N',N'-Tetramethylethylenediamine (TMEDA) complex is an effective catalyst for 1,1'-binaphthyl-2,2'-diol (BINOL) synthesis [26].…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Chiral Cu(II) salen complexes catalyzed aerobic oxidative biaryl coupling-probing the reaction by EPR

2010

View full text Add to dashboard Cite

Section: Stereoselectivity Of Biaryl Couplingsupporting

confidence: 90%

Section: Introductionmentioning

confidence: 99%

Chiral Cu(II) salen complexes catalyzed aerobic oxidative biaryl coupling-probing the reaction by EPR

2010

View full text Add to dashboard Cite

“…Enantiomerically pure diaza-cis-decalin was prepared as previously described. [25] The Cu-A C H T U N G T R E N N U N G (TMEDA)Cl(OH) catalyst was prepared [26] and used in the oxidative biaryl coupling reactions to prepare the racemic samples of the biaryl products.…”

Section: Experimental Section General Considerationsmentioning

confidence: 99%

Asymmetric Total Synthesis of Nigerone and ent‐Nigerone: Enantioselective Oxidative Biaryl Coupling of Highly Hindered Naphthols

et al. 2007

View full text Add to dashboard Cite

An enantioselective synthesis of the chiral bisnaphthopyrone natural product nigerone and its enantiomer, ent-nigerone, has been realized. The use of constrained 2-naphthol substrates was critical to producing highly functionalized chiral 1,1'-binaphthols via asymmetric oxidative biaryl coupling with 1,5-diaza-cis-decalin copper complexes. The final natural product was formed via a key eight-step isomerization process of the coupling product, bisisonigerone, and proceeded with retention of the biaryl configuration. The axial configurations of bisisonigerone and nigerone were definitively established by a combination of circular dichroism (CD) measurements and quantum chemical CD calculations.

show abstract

“…49,50) Catalytic asymmetric preparation of BINOL systems has continued to attract the attention of many researchers. [51][52][53][54][55][56][57][58][59][60][61] The asymmetric oxidative coupling of 2-naphthol molecules is one of the most useful methods for synthesis of optically pure BINOL derivatives. Vanadium-mediated couplings, which occur via a favorable one-electron phenolic oxidation, proceed under mild reaction conditions and tolerate many functional groups, with the further advantage that only water is formed as side product.…”

mentioning

confidence: 99%

Development of Dinuclear Vanadium Catalysts for Enantioselective Coupling of 2-Naphthols via a Dual Activation Mechanism

Takizawa

2009

CHEMICAL & PHARMACEUTICAL BULLETIN

View full text Add to dashboard Cite

Catalytic asymmetric reactions are among the most powerful synthetic methods to obtain optically active compounds.1,2) Recent challenges focus on the development of asymmetric catalysts for carbon-carbon bond-forming reactions with high activity and broad substrate generality, which lead to practical, efficient, and environmentally benign chemical syntheses. Dual activation systems for substrates such as nucleophiles and electrophiles lead to enhanced reaction rates and more specific control of the transition structure with respect to the catalyst's asymmetric environment. Dual activation catalyses can be classified into three categories ( Fig. 1): Type 1) dual activation using two different kinds of catalysts [3][4][5][6][7][8][9][10][11][12] ; Type 2) conjugated-type dual activation with a functional group such as a phosphate which has both acidic and basic sites in one functionality [13][14][15] ; and Type 3) dual activation by two catalytic sites in a single catalyst. For efficient dual activation of the substrates, a balance between these two functionalities in the catalyst is required. For example, in an acid-base type catalyst the selfquenching reaction of acidic and basic moieties on the catalyst can lead to its inactivation.We postulated that a chiral complex possessing two identical metal centers in a single molecule, which could activate two substrates simultaneously in a homolytic coupling reaction of 2-naphthol molecules, would enhance the reaction rate with high enantioselectivity. To achieve the new dual activation catalysis in an oxidative coupling reaction, we designed the catalyst (R a ,S,S)-1 42) bearing two active sites attached to a binaphthyl skeleton, taking advantage of the activation entropy (Fig. 2). Activation entropy strongly con- Development of Dinuclear Vanadium Catalysts for Enantioselective Coupling of 2-Naphthols via a Dual Activation MechanismShinobu TAKIZAWA This review describes our recent efforts in the development of chiral dinuclear vanadium complexes which work as dual activation catalysts for oxidative coupling of 2-naphthols. A chiral dinuclear vanadium(IV) complex (R a ,S,S)-1a possessing (S)-tert-leucine moieties at the 3,3 -positions of the (R)-binaphthyl skeleton was developed, and found to promote oxidative coupling of 2-naphthol to afford (S)-1,1 -bi-2-naphthol (BINOL) with 91% ee. To verify the dual activation mechanism, mononuclear vanadium(IV) complex (S)-10 was also prepared. Kinetic analysis revealed that the reaction rate of oxidative coupling of 2-naphthol promoted by (R a ,S,S)-1a is 48.3 times faster than that of (S)-10. In the coupling reaction, the two vanadium metals in the chiral complex activate two molecules of 2-naphthol simultaneously achieving a high reaction rate with high enantiocontrol. Since the dinuclear vanadium(IV) complex was found to be readily oxidized to afford a corresponding vanadium(V) species during preparation in air, a new synthetic procedure using VOCl 3 and a convenient one-pot procedure using VOSO 4 under O 2 have been applie...

show abstract

Enantioselective Synthesis of Binaphthol Derivatives by Oxidative Coupling of Naphthol Derivatives Catalyzed by Chiral Diamine·Copper Complexes

Cited by 315 publications

References 28 publications

Chiral Cu(II) salen complexes catalyzed aerobic oxidative biaryl coupling-probing the reaction by EPR

Chiral Cu(II) salen complexes catalyzed aerobic oxidative biaryl coupling-probing the reaction by EPR

Asymmetric Total Synthesis of Nigerone and ent‐Nigerone: Enantioselective Oxidative Biaryl Coupling of Highly Hindered Naphthols

Development of Dinuclear Vanadium Catalysts for Enantioselective Coupling of 2-Naphthols via a Dual Activation Mechanism

Contact Info

Product

Resources

About