- Novel two-phase oxidative cross-coupling of the two-component molecular crystal of 2-naphthol and 2-naphthylamine
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Two-phase reaction of a two-component molecular crystal of 2-naphthol and 2-naphthylamine suspended in aqueous Fe3+ solutions gives a cross-coupling product, 2-amino-2′-hydroxy-1,1′-binaphthalene, with good selectivity.
- Ding, Kuiling,Xu, Qiguo,Wang, Yang,Liu, Jinxia,Yu, Zhengyan,Du, Baoshi,Wu, Yangjie,Koshima, Hideko,Matsuura, Teruo
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- Mechanistic Insights into the FeCl3-Catalyzed Oxidative Cross-Coupling of Phenols with 2-Aminonaphthalenes
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The selective FeCl3-catalyzed oxidative cross-coupling reaction between phenols and primary, secondary, and tertiary 2-aminonaphthalene derivatives was investigated. The generality of this scalable method provides a sustainable alternative for preparing N,O-biaryl compounds that are widely used as ligands and catalysts. Based on a comprehensive kinetic investigation, a catalytic cycle involving a ternary complex that binds to both the coupling partners and the oxidant during the key oxidative coupling step is postulated. Furthermore, the studies showed that the reaction is regulated by off-cycle acid-base and ligand exchange processes.
- Vershinin, Vlada,Forkosh, Hagit,Ben-Lulu, Mor,Libman, Anna,Pappo, Doron
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- A general and facile approach for the synthesis of 2'-functionalized 1,1'-binapthyl-2-ols
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A facile and efficient protocol for the synthesis of 2'-functionalized 1,1'-binaphthyl-2-ols has been developed. The C,O-dilithio reagent (2) generated by the reductive ring-opening of binaphthofuran (1) with lithium was treated with the corresponding electrophiles to give 2'-functionalized 1,1'-binaphthyl-2-ols including the halides (3), amine (4), acid (5), aldehyde (6), carbonate (7) or phosphonate (8), respectively, in moderate to good yields.
- Xie, Xiaomin,Ding, Lina,Ni, Gang,Zhang, Zhaoguo,Gao, Jinsheng
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- Chiral enrichment of 2-amino-2'-hydroxy-1,1'-binaphthyl
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A new synthetic procedure for the formation of 2-amino-2'-hydroxy-1,1'- binaphthyl, and a new purification procedure through the formation of Schiff bases, purification of the Schiff bases, and breakdown of the Schiff bases through amine exchange, are described. Through the new purification procedure, greater than 99% purity of the compound can be obtained easily and reliably. A set of procedures were examined to compare the efficiency and reliability to resolve 2-amino-2'-hydroxy-1,1'-binaphthyl into enantiomers. A new procedure was discovered to enrich enantiomeric excess from less than 10% to 95-99% in one step. Even a racemic mixture from an achiral procedure can be enriched to 67% e.e. in about 4% yield. The X-ray crystal structure of the racemic mixture [rhombohedral, space group Iba2, a=15.718(2) A, b=21.703(2) A, c=8.5398(9) A, V=2913.2(5) A3, RI=0.0705, Z=8, d(calcd)=1.301 g/cm3, F(000)=1200 e] was solved to elucidate the intriguing behavior of this compound.
- Mahmoud, Hussein,Han, Ying,Segal, Brent M.,Cai, Lisheng
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- A practical synthesis of 2-amino-2′-hydroxy-1,1′-binaphthyl (NOBIN)
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A practical synthesis of 2-amino-2′-hydroxy-1,1′-binaphthyl (NOBIN) was realized from BINOL through a single step. Its facile purification procedure makes the process amenable for large scale synthesis of NOBIN.
- K?rber, Karsten,Tang, Wenjun,Hu, Xinquan,Zhang, Xumu
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- Enantiodivergent Kinetic Resolution of 1,1′-Biaryl-2,2′-Diols and Amino Alcohols by Dipeptide-Phosphonium Salt Catalysis Inspired by the Atherton–Todd Reaction
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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.
- Chen, Yuan,Fang, Siqiang,Pan, Jianke,Ren, Xiaoyu,Tan, Jian-Ping,Wang, Tianli,Zhang, Hongkui
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p. 14921 - 14930
(2021/05/10)
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- Method for resolving chiral compound
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The invention relates to the field of organic chemistry, and in particular, relates to a method for resolving a chiral compound. The method for resolving the chiral compound provided by the inventioncomprises the step of carrying out addition reaction on
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Paragraph 0077-0081
(2020/07/27)
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- A Versatile Method for Kinetic Resolution of Protecting-Group-Free BINAMs and NOBINs through Chiral Phosphoric Acid Catalyzed Triazane Formation
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A versatile kinetic resolution of protecting-group-free BINAMs and NOBINs has been realized through chiral phosphoric acid catalyzed triazane formation with azodicarboxylates. A series of mono-N-protected and unprotected BINAMs, diphenyl diamines and NOBIN derivatives could be kinetically resolved with excellent performances (with s factor up to 420). The gram-scale reactions and facile derivatizations of the chiral products demonstrate the potential of these methods in the asymmetric synthesis of chiral catalysts and ligands.
- Jiang, Qianwen,Liu, Wei,Yang, Xiaoyu
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supporting information
p. 23598 - 23602
(2020/10/23)
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- Bianthryl-based organocatalysts for the asymmetric Henry reaction of fluoroketones
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We have developed a catalytic system based on bianthrylbis(thiourea) for the asymmetric Henry reaction of fluoroketones and nitroalkanes that resulted from the screening of a library containing 31 chiral non-racemic organocatalysts. The corresponding adducts were isolated in up to 6 times shorter reaction time in comparison with the previously published organocatalysts. High levels of stereocontrol have been generally observed, with measured product enantiomeric excesses up to 97% and diastereomeric ratio 3:2 (anti/syn). The above-mentioned catalysts have been successfully applied to the total asymmetric synthesis of CF3-tethered (S)-halostachines, which has proved that this method constitutes an easy entry to similar enantiopure compounds.
- Otevrel, Jan,Svestka, David,Bobal, Pavel
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supporting information
p. 5244 - 5248
(2019/06/07)
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- Isothiourea-Catalysed Regioselective Acylative Kinetic Resolution of Axially Chiral Biaryl Diols
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An operationally simple isothiourea-catalysed acylative kinetic resolution of unprotected 1,1′-biaryl-2,2′-diol derivatives has been developed to allow access to axially chiral compounds in highly enantioenriched form (s values up to 190). Investigation of the reaction scope and limitations provided three key observations: i) the diol motif of the substrate was essential for good conversion and high s values; ii) the use of an α,α-disubstituted mixed anhydride (2,2-diphenylacetic pivalic anhydride) was critical to minimize diacylation and give high selectivity; iii) the presence of substituents in the 3,3′-positions of the diol hindered effective acylation. This final observation was exploited for the highly regioselective acylative kinetic resolution of unsymmetrical biaryl diol substrates bearing a single 3-substituent. Based on the key observations identified, acylation transition state models have been proposed to explain the atropselectivity of this kinetic resolution.
- Qu, Shen,Greenhalgh, Mark D.,Smith, Andrew D.
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supporting information
p. 2816 - 2823
(2019/02/05)
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- CARBAZOLE DERIVATIVE AND BIPHENYL DERIVATIVE PRODUCTION METHOD AND NOVEL BIPHENYL DERIVATIVE
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PROBLEM TO BE SOLVED: To provide a method for high-yield mass production of a carbazole derivative by a simple process using inexpensive materials. SOLUTION: A method for producing a carbazole derivative represented by general formula (3) comprises reacting an aminating agent with a 2,2'-dihydroxybiphenyl derivative represented by general formula (1). SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
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Paragraph 0048-0053; 0061
(2019/05/21)
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- One-pot heterocyclic ring closure of 1,1′-bi-2-naphthol to 7H-dibenzo[c,g]carbazole
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An operationally simple ring closure of racemic 1,1′-bi-2-naphthol (BINOL) yielded the heterocyclic aromatic compound 7H-dibenzo[c,g]carbazole (DBC). This one-pot method gave a good conversion and is suitable for gram-scale synthesis. DBC derivatives have high thermal durability, amorphous and crystalline structures with unique morphological properties, and semi-conducting behavior with potential applications in organic electronics.
- Hassan, Fathy,Kawamoto, Masuki,Salikolimi, Krishnachary,Hashizume, Daisuke,Hirose, Takuji,Ito, Yoshihiro
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supporting information
p. 99 - 102
(2017/12/28)
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- Fluxionally chiral DMAP catalysts: Kinetic resolution of axially chiral biaryl compounds
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Can organocatalysts that incorporate fluxional groups provide enhanced selectivity in asymmetric transformations? To address this issue, we have designed chiral 4-dimethylaminopyridine (DMAP) catalysts with fluxional chirality. These catalysts were found
- Ma, Gaoyuan,Deng, Jun,Sibi, Mukund P.
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supporting information
p. 11818 - 11821
(2015/03/13)
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- Synthesis of a tridentate ligand for use in TiIV-catalyzed acetate aldol addition reactions
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A facile, practical synthesis and resolution of (±) -2′-amino-[1,1′-binaphthalen]-2-ol (1) is described, as well as the preparation of the tridentate Schiff base ligand 2 derived from condensation of 1 with 3-bromo-5-(tert-butyl)salicylaldehyde, which has been used in catalytic enantioselective acetate aldol addition reactions.
- Singer, Robert A.,Brock, Jane R.,Carreira, Erick M.
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p. 1040 - 1044
(2007/10/03)
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- Ligands based on chiral 2-amino-2′-hydroxy-1,1′-binaphthyl and related frameworks for asymmetric catalysis
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The present invention includes array of new chiral ligands that are optically active or racemic. These ligands are bidentate, tridentate, tetradentate or pentadentate ligands which include P-P, P-N, N-N, mixed P-N, Schiff base or carbene sites. The present invention further includes a catalyst prepared by a process, which includes contacting a transition metal salt, or a complex thereof, and a ligand according to the present invention. The present invention still further includes a process for preparation of an asymmetric compound. In this process, a substrate capable of forming an asymmetric product by an asymmetric reaction and a catalyst according to the present invention are contacted to produce an asymmetric product. Transition metal complexes with these ligands are effective catalysts for asymmetric reactions. Applicant has discovered that asymmetric products can be prepared using the chiral catalysts according to the present invention in enantioselective reactions, such as hydrogenation, hydroformylation, Michael addition, Heck reaction, Aldol reaction, allylic alkylation, cyclopropanation, epoxidation, and olefin metathesis.
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- Selective Cross-Coupling of 2-Naphthol and 2-Naphthylamine Derivatives. A Facile Synthesis of 2,2',3-Trisubstituted and 2,2',3,3'-Tetrasubstituted 1,1'-Binaphthyls
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The novel 1,1'-binaphthyls with OH and/or NHR (R = H or Ph) groups in the 2,2'-positions and with additional methoxycarbonyl group(s) in the 3- or 3,3'-positions (13-18) have been synthesized from their respective precursors 1-5 by the CuCl2/t-BuNH2-mediated oxidative cross-coupling.In most cases, the chemoselectivity was good, and the cross-coupled products 11-18 were obtained in fair to excellent yields.Binaphthyls 6-10, resulting from the selfcoupling, and carbazoles 19-23 have been identified as byproducts.Ab initio calculations and electrochemical measurements have been employed to account for the observrd selectivity.
- Smrcina, Martin,Vyskocil, Stepan,Maca, Bohumil,Polasek, Miroslav,Claxton, Thomas A.,et al.
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p. 2156 - 2163
(2007/10/02)
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