Chiral dinuclear vanadium(v) catalysts for oxidative coupling of 2-naphthols

Takizawa, Shinobu; Katayama, Tomomi; Kameyama, Chiaki; Onitsuka, Kiyotaka; Suzuki, Takayoshi; Yanagida, Takeshi; Kawai, Tomoji; Sasai, Hiroaki

doi:10.1039/b717068h

Cited by 66 publications

(33 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The biquinone ( S )- 2 , in turn, could be obtained by selective oxidation of ( S )- 3 . Asymmetric biaryl coupling of 4 with a dinuclear chiral vanadium catalyst, 8 followed by methylation and deprotection would provide ( S )- 3 .…”

Section: Resultsmentioning

confidence: 99%

Structural Reassignment of a Marine Metabolite from a Binaphthalenetetrol to a Tetrabrominated Diphenyl Ether

Podlesny

Kozlowski

2012

J. Nat. Prod.

View full text Add to dashboard Cite

The structure of a reported natural product isolate has been revised from (S)-2,2′-dimethoxy-[1,1′-binaphthalene]-5,5′,6,6′-tetraol to a known tetrabrominated diphenyl ether. After total synthesis of the reported binaphthalenetetrol was accomplished via a key reduction of a binaphtho-ortho-quinone, comparison of the physical properties and NMR spectroscopic data of the synthetic material indicated that the structure of the natural product isolate was incorrect. Evaluation of the authentic natural product suggested the structure is a tetrabrominated diphenyl ether, likely 3,5-dibromo-2-(3,5-dibromo-2-methoxyphenoxy)phenol.

show abstract

Section: Resultsmentioning

confidence: 99%

Structural Reassignment of a Marine Metabolite from a Binaphthalenetetrol to a Tetrabrominated Diphenyl Ether

Podlesny

Kozlowski

2012

J. Nat. Prod.

View full text Add to dashboard Cite

show abstract

“…Up to 98% ee were reached using ligands 110 and up to 97% ee using ligand 111 [181,182]. Using ligand 110f with R = sec-Bu, a few chiral binaphthol syntheses could be optimized with great efficiency, leading to the expected compounds with greater than 98% ee and excellent yields gave binaphthols with the opposite axial chirality [184,185,186,187]. Finally, they compared the catalytic activities of complex 112 and of the corresponding mononuclear version 116 ( Figure 6.7).…”

Section: Reactions With Other Metalsmentioning

confidence: 97%

Synthesis of axially chiral biaryl compounds by asymmetric catalytic reactions with transition metals

Loxq

Manoury

Poli

et al. 2016

Coordination Chemistry Reviews

295

View full text Add to dashboard Cite

Please cite this article as: P. Loxq, E. Manoury, R. Poli, E. Deydier, A. Labande, Synthesis of axially chiral biaryl compounds by asymmetric catalytic reactions with transition metals, Coordination Chemistry Reviews (2015), http://dx. AbstractAxially chiral biaryl structures are unique systems encountered in various synthetic compounds such as BINAP and BINOL, polymers, but also in natural products presenting a pharmaceutical interest such as Vancomycin, Steganacin or Korupensamine. The axial chirality of these products, so-called atropisomerism, is induced by the restricted rotation around the aryl-aryl bond. This review will summarize the different strategies imagined by chemists to control such chirality, focusing on asymmetric catalytic processes with transition metals. Only transition metal complexes bearing chiral ligands will be considered and the core of this review will consist of the enantioselective coupling of two achiral substrates. Highlights 1. A review on the synthesis of axially chiral biaryls by asymmetric catalysis 2. Exhaustive description of chiral ligands used in the palladium-catalyzed SuzukiMiyaura cross-coupling reaction 3. Emerging reactions such as asymmetric direct C-H functionalization are presented 4. Asymmetric [2+2+2] cycloadditions catalyzed by group 9 transition metals are included

show abstract

“…This procedure gave highly active 2, which was identical to the catalyst prepared by the previous method using VOCl 3 for complexation. 45) The use of 2 prepared by the one-pot procedure was found to promote coupling, affording (S)-BINOL in 91% yield and 82% ee at 30°C in 24 h under air. 79) …”

Section: One-pot Preparation Of Chiral Dinuclear Vanadium(v) Complexmentioning

confidence: 99%

“…Although we independently developed dinuclear vanadium(IV) catalysts and dinuclear vanadium(V) catalysts for enantioselective oxidative coupling of 2-naphthols, [44][45][46][47][48] the preparation procedure for dinuclear vanadium(IV) catalysts is similar to that of Gong's catalysts [66][67][68] except for the use of 2.0-2.2 eq of vanadyl sulfate in EtOH-tetrahydrofuran (THF)-H 2 O for the complexation. Even though the absolute configurations of the components of the catalysts are the same, the absolute configurations of the major products were opposite to each other (Table 5).…”

Section: Comparison Of Our Dinuclear Vanadium(iv) and (V) Catalysts Wmentioning

confidence: 99%

“…43) This review presents our recent research on development of chiral dinuclear vanadium complexes which work as dual activation catalysts for oxidative coupling of 2-naphthols. [44][45][46][47][48] The synthesis of optically pure 1,1Ј-bi-2-naphthol (BINOL) derivatives is of importance because these moieties are used as chiral ligands and auxiliaries for a wide range of organic functional transformations. 49,50) Catalytic asymmetric preparation of BINOL systems has continued to attract the attention of many researchers.…”

mentioning

confidence: 99%

See 1 more Smart Citation

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

Takizawa

2009

CHEMICAL & PHARMACEUTICAL BULLETIN

Self Cite

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

Chiral dinuclear vanadium(v) catalysts for oxidative coupling of 2-naphthols

Abstract: Preparation and structural analysis of chiral dinuclear vanadium(v) catalysts with high catalytic activity for the oxidative coupling of 2-naphthols are described.

Cited by 66 publications

References 36 publications

Structural Reassignment of a Marine Metabolite from a Binaphthalenetetrol to a Tetrabrominated Diphenyl Ether

Structural Reassignment of a Marine Metabolite from a Binaphthalenetetrol to a Tetrabrominated Diphenyl Ether

Synthesis of axially chiral biaryl compounds by asymmetric catalytic reactions with transition metals

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

Contact Info

Product

Resources

About