- Hydrophilic interior between hydrophobic regions in inverse bilayer structures of cation-1,1′-binaphthalene-2,2′-diyl phosphate salts
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A series of 1,1′-binaphthalene-2,2′-diyl phosphate (BNPPA -) salts have been synthesized. Their crystal packings show a separation of the hydrophobic naphthyl and hydrophilic (RO)2PO 2- phosphate/cation/solvate regions. Hydrogen bonding in the latter is the driving force for "inverse bilayer" formation, with a hydrophilic interior exposing the hydrophobic binaphthyl groups to the exterior. Stacking of the inverse bilayers occurs less through π-π and more through CH...π interactions between the naphthyl groups, which correlates with the formation of thin crystal plates along the stacking direction. Cations used with R- or rac-BNPPA- are protonated isonicotin-1-ium amide (1), isonicotin-1-ium acid (2), guanidinium (3), the metal complexes trans-tetraammine-dimethanol-copper(II) (4), trans-diaqua-tetramethanol-copper(II) (5) and cis-diaqua-bis(ethylene diamine)-nickel(II) (6). Crystallization occurs with inclusion of water and methanol solvent molecules, except in 2. Starting from R-BNPPA, inversion takes place with calcium acetate to give 1 as the racemate. 2 is crystallized as the R-BNPPA salt. The inversion-symmetrical complex trans-[Cu(H2O) 2(CH3OH)4]2+ in 5 has Cu-OH 2 bond lengths of 1.937(4) A, and Cu-O(methanol) of 2.112(4) and 2.167(4) A, corresponding to a compressed tetragonal geometry. the Royal Society of Chemistry the Centre National de la Recherche Scientifique 2006.
- Dorn, Thomas,Chamayou, Anne-Christine,Janiak, Christoph
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Read Online
- FUSED RING PYRIMIDONE DERIVATIVES FOR USE IN THE TREATMENT OF HBV INFECTION OR OF HBV-INDUCED DISEASES
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Provided are compounds according to any of Formula (I-1) to (I-7), pharmaceutical compositions comprising at least one of said compounds, their use as a medicament, and their use in treating chronic hepatitis B virus (HBV) infection. Methods for preparing compounds according to any of Formula (I-1) to (I-7) are also provided.
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Page/Page column 100-101; 125; 127; 230-232; 239-240; 279-280
(2022/04/03)
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- Flash production of organophosphorus compounds in flow
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Flow synthesis techniques have received a significant amount of attention due to their high productivity. However, when reaction condition is heterogeneous, it is usually difficult to adapt it to flow synthesis. Herein, by selecting appropriate reagents, the synthesis of phosphate esters, which is commonly heterogeneous, was made homogeneous, enabling synthesis in flow systems. In addition, reaction rate was accelerated compared to the batch system. It was demonstrated that not only can the high productivity of flow synthesis be achieved in flow, but also high productivity can be achieved by accelerating the reaction. Finally, we demonstrated the synthesis of the Akiyama-Terada catalyst, a chiral organocatalysts, in a short period.
- Nagaki, Aiichiro,Tamaki, Takashi
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supporting information
(2021/09/09)
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- Asymmetric ketone hydroboration catalyzed by alkali metal complexes derived from BINOL ligands
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The ability of alkali metal complexes featuring functionalized BINOL-derived ligands to catalyze ketone hydroboration reactions was explored. The reduced products were formed in excellent yields and with variable enantioselectivities dependent upon the nature of the ligand and the alkali metal cation.
- Carden, Jamie L.,Melen, Rebecca L.,Newman, Paul D.,Ruddy, Adam J.,Willcox, Darren
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p. 2417 - 2420
(2020/03/05)
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- Synthesis of new C3 symmetric amino acid- and aminoalcohol-containing chiral stationary phases and application to HPLC enantioseparations
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We recently reported a new C3-symmetric (R)-phenylglycinol N-1,3,5-benzenetricarboxylic acid-derived chiral high-performance liquid chromatography (HPLC) stationary phase (CSP 1) that demonstrated better results as compared to a previously described N-3,5-dintrobenzoyl (DNB) (R)-phenylglycinol-derived CSP. Over a decade ago, (S)-leucinol, (R)-phenylglycine, and (S)-leucine derivatives were used as the starting materials of 3,5-DNB-based Pirkle-type CSPs for chiral separation. In this study, three new C3-symmetric CSPs (CSP 2, 3, and 4) were prepared by combining the ideas and results mentioned above. Here we describe the synthetic procedures and applications of the new C3-symmetric CSPs (CSP 2–CSP 4).
- Yu, Jeongjae,Armstrong, Daniel W.,Ryoo, Jae Jeong
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- Diquats with Robust Chirality: Facile Resolution, Synthesis of Chiral Dyes, and Application as Selectors in Chiral Analysis
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Diquats with extremely high racemization barriers with ΔG≠theor of 233 kJ mol?1 at 180 °C are described. Reported configurational robustness is due to a combination of two structural features: the rigid o-xylylene tether connecting the nitrogen atoms and the presence of two substituents in the bay region of the bipyridinium scaffold. The straightforward synthesis of diquats, plus facile resolution and derivatization make them attractive for chiral application studies. This is demonstrated by: 1) synthesis of the first non-racemic diquat dyes with pronounced chiroptical properties, and 2) capability of diquats to interact stereospecifically with chiral molecules. This suggests potential for diquat derivatives to be used as chiral selectors in separation methods.
- Talele, Harish R.,Koval, Du?an,Severa, Luká?,Reyes-Gutiérrez, Paul E.,Císa?ová, Ivana,Sázelová, Petra,?aman, David,Bednárová, Lucie,Ka?i?ka, Václav,Teply, Filip
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supporting information
p. 7601 - 7604
(2018/06/11)
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- Chiral separation on various modified amino alcohol-derived HPLC chiral stationary phases
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3,5-Dinitrobenzoyl chloride was previously used for the preparation of (R)-phenylglycinol- and (S)-leucinol-derived chiral stationary phases. In this study, 3,5-bis(trifluoromethyl)benzoyl chloride, 2-furoyl chloride, 2-theonyl chloride, 10,11-dihydro-5H-dibenzo[b,f]azepine-5-carbonyl chloride, diphenylcarbamoyl chloride, and 1-adamantanecarbonyl chloride were used to prepare six new phenylglycinol-derived chiral stationary phases (CSPs) and five new leucinol-derived CSPs. Using these 11 CSPs, chiral separation of nine π-acidic amino acid derivatives and five π-basic compounds was performed, and the separation results were compared. An adamantyl-derived CSP showed good separation.
- Yu, Jeongjae,Lee, Jung Mi,Ryoo, Jae Jeong
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p. 276 - 281
(2016/03/19)
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- Direct Asymmetric Friedel-Crafts Reaction of Naphthols with Acetals Catalyzed by Chiral Bronsted Acids
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The Friedel-Crafts method synthesis of chiral ethers from various acetals and naphthols catalyzed by chiral Bronsted acids with acetic acid as an effective additive is described. We found that the chiral phosphoric acid (R)-TRIP could efficiently catalyze the asymmetric Friedel-Crafts reaction of naphthols with acetals affording chiral ethers in good enantioselectivity and yield.
- Qin, Long,Wang, Pei,Zhang, Yixin,Ren, Zhengxiang,Zhang, Xin,Da, Chao-Shan
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supporting information
p. 571 - 574
(2016/03/01)
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- Synthesis of novel chiral phosphoric acid-bearing two acidic phenolic hydroxyl groups and its catalytic evaluation for enantioselective Friedel-Crafts alkylation of indoles and enones
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A novel chiral phosphoric acid catalyst bearing two acidic phenolic hydroxyl groups was synthesized. Its catalytic activity as a chiral Br?sted acid has been examined in the enantioselective Friedel-Crafts alkylation of indoles and enones as a model reaction. In comparison with the other chiral phosphoric acid catalysts, the reaction catalyzed by the novel chiral catalyst afforded the desired 3-substituted indoles in a higher enantioselectivity (up to 69% ee).
- Liu, Xiong-Li,Yu, Zhang-Biao,Pan, Bo-Wen,Chen, Lin,Feng, Ting-Ting,Zhou, Ying
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p. 628 - 634
(2015/03/30)
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- Enantiomeric separations of chiral sulfonic and phosphoric acids with barium-doped cyclofructan selectors via an ion interaction mechanism
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New cyclofructan-6 (CF6)-based chiral stationary phases (CSPs) bind barium cations. As a result, the barium-complexed CSPs exhibit enantioselectivity toward 16 chiral phosphoric and sulfonic acids in the polar organic mode (e.g., methanol or ethanol mobile phase containing a barium salt additive). Retention is predominantly governed by a strong ionic interaction between the analyte and the complexed barium cation as well as hydrogen bonding with the cyclofructan macrocycle. The log k versus log [X], where [X] = the concentration of the barium counteranion, plots for LARIHC-CF6-P were linear with negative slopes demonstrating typical anion exchange behavior. The nature of the barium counteranion also was investigated (acetate, methanesulfonate, trifluoroacetate, and perchlorate), and the apparent elution strength was found to be acetate > methanesulfonate > trifluoroacetate > perchlorate. A theory based upon a double layer model was proposed wherein kosmotropic anions are selectively adsorbed to the cyclofructan macrocycle and attenuate the effect of the barium cation. van't Hoff studies for two analytes were conducted on the LARIHC-CF6-P for three of the barium salts (acetate, trifluoroacetate, and perchlorate), and the thermodynamic parameters governing retention and enantioselectivity are discussed. Interestingly, for the entropically driven separations, enantiomeric selectivity can increase at higher temperatures, even with decreasing retention.
- Smuts, Jonathan P.,Hao, Xin-Qi,Han, Zhaobin,Parpia, Curran,Krische, Michael J.,Armstrong, Daniel W.
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p. 1282 - 1290
(2014/02/14)
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- Chiral synthetic equivalents of 2-cyanoethyl tetraisopropylphosphorodiamidite: Application to the synthesis and resolution of chiral phosphoric acids
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Four synthetic equivalents of (iPr2N)2P-OCH 2CH2CN (1) have been prepared from readily available enantiomerically pure β-hydroxynitriles as well as from chiral β-hydroxy esters. To demonstrate their possible use
- Isaac, Kevin,Stemper, Jeremie,Retailleau, Pascal,Betzer, Jean-Francois,Marinetti, Angela
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p. 4099 - 4106
(2014/07/08)
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- Synthesis, structural analysis, and catalytic properties of tetrakis(binaphthyl or octahydrobinaphthyl phosphate) dirhodium(II,II) complexes
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The X-ray structural analyses of homoleptic Rh(II) complexes made of enantiopure (R)-1,1′-binaphthyl and (R)-(5,5′,6,6′,7,7′, 8,8′-octahydro)binaphthyl phosphate ligands are for the first time presented. The possibility to introduce halogen atoms at the 3,3′-positions is also reported. The isolated dirhodium complexes were further tested as catalysts (1 mol %) in enantioselective cyclopropanations and Si-H insertion reactions, affording chiral cyclopropanes and silanes in good yield but moderate enantioselectivity (ee max 63%).
- Hrdina, Radim,Guenee, Laure,Moraleda, Delphine,Lacour, Jeroime
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p. 473 - 479
(2013/03/28)
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- Organocatalytic asymmetric synthesis of propargylamines with two adjacent stereocenters: Mannich-type reactions of in situ generated C-alkynyl imines with β-keto esters
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Side by side: The title reaction is catalyzed by the chiral Bronsted acid (S)-1, and affords hitherto less accessible chiral propargylamines, having two adjacent stereocenters, in good to excellent diastereo- and enantioselectivities. Boc=tert-butoxycarbonyl. Copyright
- Kano, Taichi,Yurino, Taiga,Maruoka, Keiji
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supporting information
p. 11509 - 11512
(2013/11/06)
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- Novel photolabile protecting group for phosphate compounds
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A novel photolabile protecting group, thiochromone S,S-dioxide, containing the diazomethyl group for protection of phosphate derivatives is described. Deprotection of the successfully protected phosphate derivatives proceeded smoothly under photoirradiation using an ultrahigh-pressure mercury lamp to recover the corresponding phosphates quantitatively, and the photoproduct derived from the thiochromone derivative showed high fluorescence intensity. Georg Thieme Verlag Stuttgart · New York.
- Zhang, Youlai,Tanimoto, Hiroki,Nishiyama, Yasuhiro,Morimoto, Tsumoru,Kakiuchi, Kiyomi
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scheme or table
p. 367 - 370
(2012/03/11)
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- Controlled/living ring-opening polymerization of ε-caprolactone catalyzed by phosphoric acid
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The bulk ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) by various phosphoric acids using phenylmethanol as the initiator was conducted. 1,1'-bi-2-Naphthol (BINOL)-based phosphoric acid was found to be an effective organocatalyst for ROP leading to polyesters at 90°C. The overall conversion to poly(ε-caprolactone) was more than 96% and poly(ε-caprolactone) with Mw of 8400 and polydispersity index of 1.13 was obtained. 1H NMR spectra of oligomers demonstrated the quantitative incorporation of the protic initiator in the polymer chains and showed that transesterification reactions did not occur to a significant extent. The controlled polymerization was indicated by the linear relationships between the number- average molar mass and monomer conversion or monomer-to-initiator ratio. In addition, the present protocol provided an easy-to-handle, inexpensive and environmentally benign entry for the synthesis of biodegradable materials as well as polyesters for biomedical applications. Science China Press and Springer-Verlag Berlin Heidelberg 2012.
- Chen, Chun Xia,Xu, Rong,Li, Bin
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p. 1257 - 1262
(2012/11/13)
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- Facile and efficient enantioselective strecker reaction of ketimines by chiral sodium phosphate
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A facile and efficient enantioselective Strecker reaction of ketimines catalyzed by a chiral alkali-metal salt has been developed. When 10 mol% BNPNa (BNP=1,1'-binaphthyl-2,2'-diylphosphate) prepared in situ and 10 mol% para-tert-butylortho-adamantylphenol (PBAP) were introduced into the reaction, up to 96% yield and up to 95% ee (ee=enantiomeric excess) were obtained. Both aliphatic and aromatic ketimines, especially sterically bulky cyclic ketimines derived from β-acetonaphthone, α-indanone, and α-tetralone were found suitable for this reaction. On the basis of the experimental results and previous reports, trimethylsilyl cyanide (TMSCN) was indicated to be the real reactive nucleophile despite the existence of PBAP, and a possible working model was proposed to explain the origin of the asymmetric induction. The facile availability of 1,1'-binaphthyl-2,2'-diylphosphoric acid (BNPH) and the simplicity of the procedure are beneficial for practical applications.
- Shen, Ke,Liu, Xiaohua,Cai, Yunfei,Lin, Lili,Feng, Xiaoming
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supporting information; experimental part
p. 6008 - 6014
(2010/02/28)
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- Chiral lithium salts of phosphoric acids as Lewis acid-base conjugate catalysts for the enantioselective cyanosilylation of ketones
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The catalytic enantioselective cyanosilylation of aromatic ketones was developed by using chiral lithium salts of (R)-BINOL- or (S)-BINAM-derived phosphoric acid compounds. In the presence of 10 mol% of chiral conjugate lithium salts, the corresponding tertiary cyanohydrins were obtained in high yields with moderate to high enantio-selectivities. This is the first efficient example of asymmetric catalysis using lithium salts of synthetically useful chiral phosphoric acid compounds. A possible catalytic mechanism and transition states are also discussed as a preliminary working hypothesis.
- Hatano, Manabu,Ikeno, Takumi,Matsumura, Tokihiko,Torii, Shinobu,Ishihara, Kazuaki
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supporting information; experimental part
p. 1776 - 1780
(2009/07/01)
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- Process for production of amines
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A process for producing an amine which is characterized by reacting an imine with a nucleophilic compound (except a trialkylsilyl vinyl ether) in the presence of a phosphoric acid derivative represented by the formula (1): wherein A1 represents a spacer; X1 and X2 represent each independently a divalent nonmetal atom or a divalent nonmetal atomic group; and Y1 is oxygen or sulfur. The invention provides a process by which amines (particularly optically active amines) useful as intermediates of medicines, agricultural chemicals, or the like can be produced without special post-treatment in high yield at high optical purity; and phosphoric acid derivatives (particularly optically active phosphoric acid derivatives) useful in the production of the amines.
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Page/Page column 48
(2008/06/13)
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- Chiral Bronsted acid catalyzed enantioselective Mannich-type reaction
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Mannich-type reaction of ketene silyl acetals with aldimines proceeded catalytically by means of a phosphoric acid diester, derived from (R)-BINOL, as a chiral Bronsted acid to afford β-amino esters with good diastereoselectivity in favor of the syn isomer and high enantioselectivity (up to 96% ee). The highest enantioselectivity was achieved by the phosphoric acid diester bearing 4-nitrophenyl groups on the 3,3′-positions of BINOL. The N-2-hydroxyphenyl group of aldimine was found to be essential for the present Mannich-type reaction. In combination with these experimental investigations, two possible monocoordination and dicoordination pathways were explored using density functional theory calculations (BHandHLYP/6-31G*). The present reaction proceeds via a dicoordination pathway through the zwitterionic and nine-membered cyclic transition state (TS) consisting of the aldimine and the phosphoric acid. The re-facial selectivity was also well-rationalized theoretically. The nine-membered cyclic structure and aromatic stacking interaction between the 4-nitrophenyl group and N-aryl group would fix the geometry of aldimine on the transition state, and the si-facial attacking TS is less favored by the steric hindrance of the 3,3′-aryl substituents.
- Yamanaka, Masahiro,Itoh, Junji,Fuchibe, Kohei,Akiyama, Takahiko
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p. 6756 - 6764
(2008/02/06)
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- Process for the resolution of racemic (R,S) -5-(2-(2-(2- ethoxyphenoxy) ethylamino)propyl)-2-methoxybenzene sulfonamide (tamsulosin), its novel R and S isomers and their salts and processes for their preparation
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An improved process is described to resolve a racemic mixture in any proportion of 5-(2-(2-(2-ethoxyphenoxy)ethylamino)propyl)-2-methoxy benzene sulfonamide as a free base or some of its salts, with BPA either S or R form to obtain enantiomerically highly pure R and S-isomer as a well characterized free base or as a salt of the title compound. Also described are novel R and S-isomers of 5-(2-(2-(2-ethoxyphenoxy) ethylamino)propyl)-2-methoxy benzene sulfonamide and their salts and the processes for their preparation.
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Page/Page column 7
(2010/10/20)
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- Chiral separations using a polypeptide and polymeric dipeptide surfactant polyelectrolyte multilayer coating in open-tubular capillary electrochromatography
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A polyelectrolyte multilayer (PEM) coating consisting of the polypeptide, poly(L-lysine) hydrobromide, poly(L-lysine) and the polymeric dipeptide surfactant, poly(sodium undecanoyl-L-leutcyl-alaninate), poly(L-SULA), is investigated as a new medium for the separation of chiral analytes in open-tubular capillary electrochromatography (OT-CEC). In this approach, a stable PEM is constructed in situ by alternative rinses of the cationic polymer poly(L-lysine) and the anionic polymer poly(L-SULA). In previous studies, the PEM coating has been constructed by use of the cationic polyelectrolyte poly (diallydimethylammonium chloride), PDADMAC. In this study, we investigate the use of a biopolymer as the cationic polyelectrolyte. The results reported here indicate an increase in selectivity and resolution when poly(L-lysine) is used as the cationic polymer in place of PDADMAC. To evaluate the chromatographic performance of the PEM coating as a chiral stationary phase, the separation of the β-blockers, labetalol and sotalol, and the binaphthyl derivatives, 1,1′-bi-2-naphthyl-2,2′-dihydrogen phosphate, 1,1′-bi-2- naphthol, and 1,1-binaphthyl-2,2′-diamine, are investigated. In addition, the effect of varying the amino acid order of the polymeric dipeptide surfactant on resolution is investigated. The number of bilayers also significantly influences the separation efficiency and resolution of enantiomers. The run-to-run and capillary-to-capillary reproducibilities are evaluated by calculating the relative standard deviations (RSDs) of the electroosmotic flow. These RSD values were found to be less than 1%. The coating is also stable and allows more than 290 runs to be performed in the same capillary. In addition, coupling of this chiral OT-CEC column with mass spectrometry is investigated.
- Kamande, Mary W.,Zhu, Xiaofeng,Kapnissi-Christodoulou, Constantina,Warner, Isiah M.
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p. 6681 - 6692
(2007/10/03)
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- Synthesis of New Alkyl Derivatives of 2,2'-Dihydroxy-1,1'-binaphthyl
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2'-Hydroxy-1,1'-binaphthyl-2-yl phosphate 4 reacts with various alkylating agents under controlled conditions to give differently alkylated phosphoric esters 5-9. The monoalkylation of binaphthol 1 with long-chain alkyl halides followed by reaction with phosphoryl chloride, propane-1,3-sultone or chlorosulfuric acid, respectively, yielded the amphiphilic binaphthyl derivatives 14-17. The compounds prepared were fully characterized by spectroscopic methods.
- Koy, Cornelia,Michalik, Manfred,Oehme, Guenther,Fischer, Christine,Tillack, Annegret,Baudisch, Hannelore,Kempe, Rhett
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p. 203 - 228
(2007/10/03)
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- CNS affecting 5-oxy-3-aminomethyl-dihydro-benzofurans and benzothiophenes
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The present invention relates to 3-aminomethyl derivatives of indane, dihydrobenzofurane, dihydrobenzothiophene, and indoline, acid addition salts thereof, isomers thereof, methods of preparation, pharmaceutical compositions and method of treating CNS-disorders such as schizophrenia, Parkinson's disease, depression, anxiety, migraine and senile dementia, or in the cure of cardiovascular diseases, by administering such a derivative.
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- Resolution of the Enantiomers of (S,R)-1,1'-Bi-2,2'-naphthylhydrogenphosphate by (1R,2R)- and (1S,2S)-2-Amino-1-(4-nitrophenyl)-propane-1,3-diol
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The resolution of the diastereoisomeric salts of the title compounds was possible in the presence of a ketone, especially acetone, which forms oxazolidines (3a-d) with the chiral bases.These oxazolidines afforded separable salts with the (S,R)-1,1'-Bi-2,2'-naphthylhydrogenphosphate (4).The structures of these salts were proved by m.s. and n.m.r. spectroscopy.
- Werner, W.,Tresselt, D.,Ihn, W.,Ziebell, G.
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p. 1031 - 1037
(2007/10/02)
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- Carbon catalyzed organic reactions: carbon promoted solvolysis of a phosphate ester derived from 1,1'-bi-2-naphtol
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Active carbons which catalyze the racemization of 1.1'-binaphthyl are not effective in racemizing the 2,2'-dihydroxyl and the 8,8'-dicarbomethoxyl derivatives of binaphthyl.The 2,2'-binaphthyl methyl phosphate ester derived from optically active 1,1'-bi-2-naphthol undergoes slow thermal racemization at 190 deg C (t1/2 100 min, ΔH(excit.) 26.1 kcal/mol, ΔS(excit.) -21 cal/mol deg) in triglyme and this racemization rate is also unaffected by active carbon.However, in the hydroxylic solvent 2-(2-ethoxyethoxy)ethanol at 130 deg C the rate of solvolysis of the phosphate ester is increased ca. tenfold by carbon blacks or decolorizing carbon at 1 mg/mL concentration.Control experiments show that the acceleration is not due to soluble impurities released by the carbons; heterogeneous catalysis, probably by acidic and/or nucleophilic functional groups on the carbon surfaces, is involved.
- Hoyano, Yumiko Y.,Pincock, Richard E.
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p. 134 - 137
(2007/10/02)
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