18531-94-7Relevant articles and documents
An improved approach to (R)-(+)-1,1'-bi-2-naphthol of 100% enantiomeric excess via a cyclic borate ester
Shan, Zixing,Cheng, Fuyong,Huang, Shiwen,Zhao, Dejie,Jing, Zhizhong
, p. 1175 - 1177 (1997)
The preparation for (R)-(+)-1,1'-bi-2-naphthol of 100% ee using cinchonine as a resolving agent via a cyclic borate ester is described.
Chiral dinuclear vanadium(v) catalysts for oxidative coupling of 2-naphthols
Takizawa, Shinobu,Katayama, Tomomi,Kameyama, Chiaki,Onitsuka, Kiyotaka,Suzuki, Takeyuki,Yanagida, Takeshi,Kawai, Tomoji,Sasai, Hiroaki
, p. 1810 - 1812 (2008)
Preparation and structural analysis of chiral dinuclear vanadium(v) catalysts with high catalytic activity for the oxidative coupling of 2-naphthols are described. The Royal Society of Chemistry.
Dual activation in oxidative coupling of 2-naphthols catalyzed by chiral dinuclear vanadium complexes
Takizawa, Shinobu,Katayama, Tomomi,Somei, Hidenori,Asano, Yasuaki,Yoshida, Tomokazu,Kameyama, Chiaki,Rajesh, Doss,Onitsuka, Kiyotaka,Suzuki, Takeyuki,Mikami, Masafumi,Yamataka, Hiroshi,Jayaprakash, Doss,Sasai, Hiroaki
, p. 3361 - 3371 (2008)
An efficient enantioselective oxidative coupling of 2-naphthol derivatives based on a concept of dual activation catalysis is realized. A chiral dinuclear vanadium(IV) complex (Ra,S,S)-1e possessing (S)-tert-leucine moieties at the 3,3′-positions of the (R)-binaphthyl skeleton was developed, which was found to promote the oxidative coupling of 2-naphthol to afford (S)-BINOL with 91% ee. To verify the dual activation mechanism, mononuclear vanadium(IV) complex (S)-8 was also prepared. Kinetic analysis revealed that the reaction rate of oxidative coupling of 2-naphthol promoted by (Ra,S,S)-1e is 48.3 times faster than that of (S)-8. The two vanadium metals in the chiral complex activate two molecules of 2-naphthol simultaneously in an intramolecular manner coupling reaction, achieving a high reaction rate with high enantiocontrol. Reaction mechanisms of the oxidative coupling reaction promoted by either vanadium(IV) or vanadium(V) complexes are also described.
Irreversible visual sensing of humidity using a cholesteric liquid crystal
Saha, Abhijit,Tanaka, Yoko,Han, Yang,Bastiaansen, Cees M.W.,Broer, Dirk J.,Sijbesma, Rint P.
, p. 4579 - 4581 (2012)
Irreversible optical sensing of humidity by a doped cholesteric liquid crystal is achieved by using a thin film of nematic host E7 with a binaphthylorthosilicate ester as dopant (guest). The film changes its color from blue (to green to orange to red) to colorless when exposed to humidity as the dopant is hydrolyzed. The Royal Society of Chemistry 2012.
Lipase-catalyzed stereoselective resolution and desymmetrization of binaphthols
Juarez-Hernandez, Marcela,Johnson, Dean V.,Holland, Herbert L.,McNulty, James,Capretta, Alfredo
, p. 289 - 291 (2003)
We have investigated the use of lipoprotein lipase enzymes from Pseudomonas sp. and Pseudomonas fluorescens for the enantioselective resolution and desymmetrization of racemic binaphthols. The reactions were carried out using a non-aqueous environment (iPr2O/acetone/vinyl acetate), and yielded mono-acetate ester products of the parent unsubstituted substrate, the 6,6′-dibromo-substrate, and the 6,6′-dimethoxy-substrate with high enantiomeric selectivity.
The rational design of novel chiral oxovanadium(IV) complexes for highly enantioselective oxidative coupling of 2-naphthols
Luo, Zhibin,Liu, Quanzhong,Gong, Liuzhu,Cui, Xin,Mi, Aiqiao,Jiang, Yaozhong
, p. 914 - 915 (2002)
Several novel chiral oxovanadium(IV) complexes have been designed and prepared for the asymmetric catalytic oxidative coupling of 2-naphthols with high enantioselectivities of 83-98% ee.
Tetrahydro-1,4-epoxynaphthalene-1-carboxylic acid: a chiral resolving agent for the resolution and absolute configuration assignment of 7,7'-disubstituted 1,1'-bi-2-naphthols
Dolsophon, Kulvadee,Ruangsupapichat, Nopporn,Soponpong, Jakapun,Sungsuwan, Suttipun,Prabpai, Samran,Kongsaeree, Palangpon,Thongpanchang, Tienthong
, p. 1113 - 1120 (2016)
Tetrahydro-1,4-epoxynaphthalene-1-carboxylic acid (THENA), was applied as a chiral derivatizing agent to resolve 7,7'-disubstituted 1,1'-bi-2-naphthol derivatives. This process is very efficient and could potentially be used as a preliminary tool to assign the absolute configuration of substituted 1,1'-bi-2-naphthols by means of a simple TLC.
Oxidative coupling of 2-naphthol to (R)/(S)-BINOL by MCM-41 supported Mn-chiral Schiff base complexes
Bania, Kusum K.,Karunakar,Satyanarayana, Lanka
, p. 33185 - 33198 (2015)
Three Mn(III)-chiral Schiff base complexes supported on MCM-41 are found to be effective reusable catalysts for enantioselective oxidation of 2-naphthol to (R)- and (S)-BINOL (1,1′ bi-2-naphthol) in the presence of oxygen. The supported Mn(III)-complexes are characterized by PXRD, FTIR, solid state-NMR, BET, and cyclic voltammetry study. The homo-coupling reaction with oxygen as the oxidant is promoted by 20 mg of Mn(III) Schiff base complexes to afford binaphthols in nearly quantitative yields with high enantioselectivity of up to 91% ee. The catalytic activities of the homogeneous and heterogeneous chiral catalyst are found to be almost similar. However, the heterogeneous counterparts are found to be advantageous in terms of recyclability and storability. Oxygen partial pressure, the nature of the solvent, temperature and the amount of catalyst affect the catalytic oxidation process. High temperature and highly polar solvent are found to have adverse effects on the catalytic oxidation process.
Synthesis of enantiopure, axially chiral, Cα-tetrasubstituted α-amino acids with binaphthyl-based crowned side chains and 3D-structural analysis of their peptides
Wright, Karen,Lohier, Jean-Fran?ois,Wakselman, Michel,Mazaleyrat, Jean-Paul,Formaggio, Fernando,Peggion, Cristina,De Zotti, Marta,Toniolo, Claudio
, p. 2307 - 2320 (2008)
The syntheses of the terminally protected, crowned, Cα-tetrasubstituted α-amino acids with only axial chirality, the two diastereomers Boc-(S)-Bip[(R)-Binol-22-C-6]-OMe and Boc-(R)-Bip[(R)-Binol-22-C-6]-OMe, and their respective enantiomers Boc-(R)-Bip[(S)-Binol-22-C-6]-OMe and Boc-(S)-Bip[(S)-Binol-22-C-6]-OMe, all derived from 2′,1′:1,2; 1″,2″:3,4-dibenzcyclohepta-1,3-diene-6-amino-6-carboxylic acid (Bip), were performed by bis-alkylation with cyclization of racemic (R+S)-Boc-[HO]2-Bip-OMe, possessing two phenolic OH groups at the 6,6′-positions of the biphenyl frame of Bip, using (+)-(R)- and (-)-(S)-Binol[(OCH2CH2)2OTs] 2 (2,2′-bis[5-tosyloxy-3-oxa-1-pentyloxy]-1,1′-binaphthyl), respectively, as the alkylating agent followed by chromatographic separation. Two series of terminally protected model peptides to the hexamer level, containing the (R)-Bip[(S)-Binol-22-C-6] residue at i and i+3 positions of the sequence, combined with either l-Ala or l-Ala/Aib, were synthesized by solution methods. Their 3D-structural analyses by FTIR absorption and NMR suggest that these peptides preferentially adopt folded secondary structures.
Effects of reaction temperature and acyl group for lipase-catalyzed chiral binaphthol synthesis
Aoyagi, Naoto,Ogawa, Naomi,Izumi, Taeko
, p. 4797 - 4801 (2006)
Candida antarctica lipase-catalyzed hydrolysis of O-butyryl-BINOL [(±)-3] or O-butyryl-6,6′-dibromo-BINOL [(±)-5] yielded optically active BINOL [(R)-1] or 6,6′-dibromo-BINOL [(R)-4] with high enantiomeric excess at 80 °C. Reaction temperature and acyl group of substrate had a great influence on the reactivity and enantioselectivity, respectively, of lipase-catalyzed hydrolysis for chiral binaphthol synthesis.
ON THE MECHANISM OF THE FORMATION OF S(-)-(1.1'-BINAPHTALENE)-2,2'-DIOL VIA COPPER(II)AMINE COMPLEXES
Brussee, J.,Groenendijk, J. L. G.,Koppele, J. M. te,Jansen, A. C. A.
, p. 3313 - 3319 (1985)
The oxidative dimerization of 2-naphtol is studied by means with several copper(II)amine complexes as oxidants.Using primary amines a chemical yield of 95percent-98percent is obtained.Using (+)-amphetamine as complexing amine a 94percent-96percent optically pure product is obtained.It is established that htis stereoselectivity is a result of selective precipitation of the copper(II)-(+)-amphetamine-(-)-binaphtol complex with a simultaneous racemization of the (+)-binaphtol.
A novel type of catalysts for asymmetric oxidative coupling of 2-naphthol
Larionov,Peregudova,Maleev,Belokon, Yu. N.
, p. 685 - 688 (2016)
Stereochemically inert, positively charged chiral octahedral complexes of CoIII and CrIII were used as catalysts for asymmetric oxidative coupling of 2-naphthol. The reaction product 1,1′-bi-2-naphthol was produced with a yield of up to 74% and enantiomeric excess of up to 22%. The reduction and oxidation potentials of a series of CoIII and CrIII cationic complexes were measured.
A surface molecularly imprinted polymer as chiral stationary phase for chiral separation of 1,1′-binaphthalene-2-naphthol racemates
Dong, Hongxing,Zhang, Danxia,Lin, Hailong,Wang, Yudan,Liu, Lijia,Zheng, Meixia,Li, Xiaobo,Zhang, Chunhong,Li, Junqing,Zhang, Peng,So, Juhyok
, p. 340 - 347 (2017)
Acrylamide (AM) was copolymerized with ethylene glycol dimethacrylate (EGDMA) in the presence of (R)-1,1′-binaphthalene-2-naphthol (BINOL) as the template molecules on the surface of silica gel by a free radical polymerization to produce a chiral stationary phase based on the surface molecularly imprinted polymer (SMIP-CSP). The SMIP-CSP showed a much better separation factor (α = 4.28) than the CSP based on the molecularly imprinted polymer (MIP-CSP) without coating on the silica gel (α = 1.96) during the chiral separation of BINOL enantiomers by high-performance liquid chromatography. The influence of the pretreatment temperature and the content of the template molecule ((R)-BINOL) of the SMIP-CSP, and the mobile phase composition on the separation of the racemic BINOL were systematically investigated.
Highly enantioselective deracemization of linear and vaulted biaryl ligands.
Zhang,Yeung, Siu-Man,Wu, Hongqiao,Heller, Douglas P,Wu, Chunrui,Wulff, William D
, p. 1813 - 1816 (2003)
[reaction: see text] A copper-mediated deracemization of the vaulted biaryl ligands VANOL and VAPOL can be readily achieved in the presence of (-)-spartiene. The optimal procedure involves the in situ generation of copper(II) and leads to the reproducible formation of (S)-VANOL and (S)-VAPOL in greater than 99% ee from the racemates. This method is superior to existing procedures for BINOL (92% ee).
Epimerization-Crystallization Method in Optical Resolution of 2,2'-Dihydroxy-1,1'-binaphthyl, and Kinetic Study
Kawashima, Masatoshi,Hirata, Reiko
, p. 2002 - 2005 (1993)
Optical resolution of 2,2'-dihydroxy-1,1'-binaphthyl (1) with (R,R)-1,2-cyclohexanediamine (2) in toluene yielded optically pure (R)-1 in a yield of 160percent based on the theoretical amount of the enantiomer contained in the racemate by selective crystallization of a less soluble complex, (R)-1*(R,R)-2, and epimerization of more soluble complex, (S)-1*(R,R)-2.Also optically pure (S)-1 was obtained with the same enantiomer of the resolving agent, (R,R)-2, in a yield of 154percent. (R,R)-1,2-Diphenyl-1,2-ethanediamine (3) was a suitable resolving agent for both 1 and 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl.Kinetic study indicated that the reversible first-order rate constants for the epimerizations of (S)-1*(R,R)-2 and (S)-1*(R,R)-3 were larger than that for the racemization of (S)-1.The activation energy and frequency factor for the epimerization of (S)-1*(R,R)-2 were 109 kJ mol-1 K-1 and 3E10 s-1, respectively, and those for (S)-1*(R,R)-3 were 96 kJ mol-1 and 1E8 s-1, while those for the racemization of (S)-1 were 85 kJ mol-1 K-1 and 9E5 s-1, respectively.
Dual activation in a homolytic coupling reaction promoted by an enantioselective dinuclear vanadium(IV) catalyst
Somei, Hidenori,Asano, Yasuaki,Yoshida, Tomokazu,Takizawa, Shinobu,Yamataka, Hiroshi,Sasai, Hiroaki
, p. 1841 - 1844 (2004)
A new concept of dual activation catalysis in homolytic coupling reaction of 2-naphthol derivatives is described. The dinuclear vanadium(IV) catalyst (R,S,S)-1a promotes the oxidative coupling reaction of 2-naphthol derivatives with high reactivity and enantioselectivity. This dual activation mechanism is supported by the fact that the reaction rate of oxidative coupling of 2-naphthol promoted by the (R,S,S)-1a is 48 times faster than that of the mononuclear complex (S)-3 and a lower catalyst loading of (R,S,S)-1a shows higher catalyst efficiency both in enantioselectivity and chemical yield.
Convenient and highly efficient chromatographic resolution of BINOL and of 6,6′-dibromo-BINOL via N(α)-Boc-tryptophan esters
Panchal, Bhavesh M.,Einhorn, Cathy,Einhorn, Jacques
, p. 9245 - 9248 (2002)
Racemic [1,1′]binaphthalenyl-2,2′-diol (BINOL, (±)-1) has been esterified with various commercially available N-protected-L-amino acids, giving the corresponding diastereomeric esters. Their TLC separation factors were highly dependent on the amino acid pattern. Diesters of (±)-1 and N(α)-Boc-tryptophan (3a) showed unusually large separation factors, which allowed their efficient separation by simple column chromatography. Removal of the tryptophan moieties under very mild conditions furnished each enantiomer of 1 in high overall yield and 100% ee. This procedure was also successful for the resolution of racemic 6,6′-dibromo-[1,1′]binaphthalenyl-2,2′-diol (6,6′-dibromo-BINOL, (±)-2).
Catalytic asymmetric coupling of 2-naphthols by chiral tridentate oxovanadium(IV) complexes
Hon, Sang-Wen,Li, Chun-Hsin,Kuo, Jen-Huang,Barhate,Liu, Yi-Hung,Wang, Yu,Chen, Chien-Tien
, p. 869 - 872 (2001)
matrix presented A series of chiral oxovanadium(IV) complexes derived from tridentate N-3,5-substituted and N-3,4-benzo- and N-5,6-benzo-salicylidene-α-amino acids can serve as efficient catalysts for the enantioselective oxidative couplings of various 3-, 6-, and 7-substituted 2-naphthols under O2. The best scenario involves the use of a vanadyl complex arising from 2-hydroxy-1-naphthaldehyde and valine (or phenylalanine) in CCl4, leading to BINOLs in good yields (75-100%) and with enantioselectivities of up to 68%.
Highly enantioselective oxidative couplings of 2-naphthols catalyzed by chiral bimetallic oxovanadium complexes with either oxygen or air as oxidant
Guo, Qi-Xiang,Wu, Zhi-Jun,Luo, Zhi-Bin,Liu, Quan-Zhong,Ye, Jian-Liang,Luo, Shi-Wei,Cun, Lin-Feng,Gong, Liu-Zhu
, p. 13927 - 13938 (2007)
The chiral bimetallic oxovanadium complexes have been designed for the enantioselective oxidative coupling of 2-naphthols bearing various substituents at C6 and/or C7. The chirality transferring from the amino acid to the axis of the biphenyl in oxovanadium complexes 2 was found to occur with the use of UV and CD spectra and DFT calculation. The homo-coupling reaction with oxygen as the oxidant was promoted by 5 mol % of an oxovanadium complex derived from L-isoleucine and achiral biphenol to afford binaphthols in nearly quantitative yields with high enantioselectivities of up to 98% ee. An oxovanadium complex derived from L-isoleucine and H8-binaphthol is highly efficient at catalyzing the air-oxidized coupling of 2-naphthols with excellent enantioselectivities of up to 97% ee. 51V NMR study shows that the oxovanadium complexes have two vanadium(V) species. Kinetic studies, the cross-coupling reaction, and HRMS spectral studies on the reaction have been carried out and illustrate that two vanadium(V) species are both involved in catalysis and that the coupling reaction undergoes a radical-radical mechanism in an intramolecular manner. Quantum mechanical calculations rationalize the importance of the cooperative effects of the axial chirality matching S-amino acids on the stereocontrol of the oxidative coupling reaction. The application of the transformation in the preparation of chiral ligands and conjugated polymers confirms the importance of the current process in organic synthesis.
Chiral oxovanadium complex catalyzed enantioselective oxidative coupling of 2-naphthols
Chu,Hwang,Wang,Uang
, p. 980 - 981 (2001)
The enantioselective oxidative coupling of 2-naphthols using 2 mol% chiral oxovanadium complex under mild conditions afforded chiral BINOLs in moderate enantioselectivity.
Regioselective remote functionalization of biaryl framework via tethered ortho-quinol intermediate
Koyama, Yasuhito,Kataoka, Hiroko,Suzuki, Keisuke,Matsumoto, Takashi
, p. 355 - 358 (2011)
An umpoled method for regioselective functionalization of biaryls is demonstrated. As a model substrate, binol was converted into a tethered ortho-quinol derivative, allowing selective installation of nucleophiles at the C4 or C3 position to give monofunctionalized binol derivatives with complete retention of the axial stereochemistry. Copyright
Enantioselective and aerobic oxidative coupling of 2-naphthol derivatives using chiral dinuclear vanadium(V) complex in water
Sako, Makoto,Takizawa, Shinobu,Yoshida, Yasushi,Sasai, Hiroaki
, p. 613 - 616 (2015)
Abstract The enantioselective oxidative coupling of 2-naphthols in water was established using dinuclear vanadium(V/IV) catalysis with O2 as the sole co-oxidant. In the vanadium-catalyzed reaction, the corresponding coupling products were obtained in good to excellent yields with up to 94% enantiomeric excess. In water, racemization of the coupling product was suppressed even at high temperature (70°C).
Efficient Optical Resolution of 2,2'-Dihydroxy-1,1'-binaphthyl and 10,10'-Dihydroxy-9,9'-biphenanthryl by Complex Formation with Novel Chiral Host Compounds Derived from Tartaric Acid
Toda, Fumio,Tanaka, Koichi,Nassimbeni, Luigi,Niven, Margaret
, p. 1371 - 1374 (1988)
2,2'-Dihydroxy-1,1'-binaphthyl and 10,10'-dihydroxy-9,9'-biphenanthryl were resolved efficiently by complex formation with novel chiral host compounds derived from tartaric acid, (R,R)-(+)-2,3-dimethoxy-N,N,N',N'-tetramethylsuccinamide and (R,R)-(+)-N,N,N',N'-tetramethyl-2,2-dimethyl-1,3-dioxolane-trans-4,5-dicarboxamide, respectively.X-Ray crystal structure of these complexes was studied.
Preparation of a novel bridged bis(β-cyclodextrin) chiral stationary phase by thiol-ene click chemistry for enhanced enantioseparation in HPLC
Gong, Bolin,Guo, Siyu,Zhang, Ning
, p. 35754 - 35764 (2021/12/02)
A bridged bis(β-cyclodextrin) ligand was firstly synthesized via a thiol-ene click chemistry reaction between allyl-ureido-β-cyclodextrin and 4-4′-thiobisthiophenol, which was then bonded onto a 5 μm spherical silica gel to obtain a novel bridged bis(β-cyclodextrin) chiral stationary phase (HTCDP). The structures of HTCDP and the bridged bis(β-cyclodextrin) ligand were characterized by the 1H nuclear magnetic resonance (1H NMR), solid state 13C nuclear magnetic resonance (13C NMR) spectra spectrum, scanning electron microscope, elemental analysis, mass spectrometry, infrared spectrometry and thermogravimetric analysis. The performance of HTCDP in enantioseparation was systematically examined by separating 21 chiral compounds, including 8 flavanones, 8 triazole pesticides and 5 other common chiral drugs (benzoin, praziquantel, 1-1′-bi-2-naphthol, Tr?ger's base and bicalutamide) in the reversed-phase chromatographic mode. By optimizing the chromatographic conditions such as formic acid content, mobile phase composition, pH values and column temperature, 19 analytes were completely separated with high resolution (1.50-4.48), in which the enantiomeric resolution of silymarin, 4-hydroxyflavanone, 2-hydroxyflavanone and flavanone were up to 4.34, 4.48, 3.89 and 3.06 within 35 min, respectively. Compared to the native β-CD chiral stationary phase (CDCSP), HTCDP had superior enantiomer separation and chiral recognition abilities. For example, HTCDP completely separated 5 other common chiral drugs, 2 flavanones and 3 triazole pesticides that CDCSP failed to separate. Unlike CDCSP, which has a small cavity (0.65 nm), the two cavities in HTCDP joined by the aryl connector could synergistically accommodate relatively bulky chiral analytes. Thus, HTCDP may have a broader prospect in enantiomeric separation, analysis and detection. This journal is
Enantiodivergent Kinetic Resolution of 1,1′-Biaryl-2,2′-Diols and Amino Alcohols by Dipeptide-Phosphonium Salt Catalysis Inspired by the Atherton–Todd Reaction
Chen, Yuan,Fang, Siqiang,Pan, Jianke,Ren, Xiaoyu,Tan, Jian-Ping,Wang, Tianli,Zhang, Hongkui
, p. 14921 - 14930 (2021/05/10)
A highly enantiodivergent organocatalytic method is disclosed for the synthesis of atropisomeric biaryls via kinetic resolution inspired by a dipeptide-phosphonium salt-catalyzed Atherton–Todd (A-T) reaction. This flexible approach led to both R- and S-enantiomers by fine-tuning of bifunctional phosphonium with excellent selectivity factors (s) of up to 1057 and 525, respectively. The potential of newly synthesized O-phosphorylated biaryl diols was illustrated by the synthesis of axially chiral organophosphorus compounds. Mechanistic investigations suggest that the bifunctional phosphonium halide catalyst differentiates between the in-situ-generated P-species in the A-T process, mainly involving phosphoryl chloride and phosphoric anhydride, thus leading to highly enantiodivergent O-phosphorylation reactions. Furthermore hydrogen bonding interactions between the catalysts and phosphorus molecules were crucial in asymmetric induction.
