- Synthesis of (±)-3,3′-diphenyl-2,2′-binaphthol via different routes using Pd and Ni as catalyst respectively
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3,3′-Biphenyl-2,2′-binaphthols (BINOLs) are precursors of phosphoric acids that are widely used as ligands and catalysts in organic reactions. In this report, two routes for the synthesis of (±)-3,3′-diphenyl BINOLs via (±)-3,3′ bis-halogenated BINOLs int
- Fu, Zhengjiang,Cao, Xihan,Hao, Guangguo,Shi, Quanqing,Cai, Hu
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p. 831 - 836
(2020/09/09)
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- Synthesis of structurally diversified BINOLs and NOBINs via palladium-catalyzed C-H arylation with diazoquinones
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Privileged biaryl frameworks, BINOL and NOBIN, were efficiently constructed with sole 1-DNQs as arylation reagents under one set of reaction conditions. The judicious selection of palladium-catalytic system plays a pivotal role in the excellent selectivities. This transformation accommodated fairly broad substrate generality for both 2-naphthol and N-Boc-2-naphthylamine and afforded the structurally diversified BINOLs and NOBIN derivatives in high efficiency. Notably, the bromo-substituents which cannot survive in conventional palladium-catalyzed reactions were well-compatible with this set of conditions, providing an effective handle for further enriching the library of BINOLs and NOBINs. Preliminary attempts on the asymmetric variant of this reaction were also performed with up to 80:20 er for BINOLs synthesis. [Figure not available: see fulltext.].
- Zhang, Ji-Wei,Jiang, Fei,Chen, Ye-Hui,Xiang, Shao-Hua,Tan, Bin
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p. 1515 - 1521
(2021/07/06)
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- INHIBITORS OF GLUCOSE TRANSPORTERS (GLUTS)
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The present invention relates to 2,6-methanobenzo[g][1]oxacin-4-onecompounds and their analog compounds and pharmaceutically acceptable salts thereof as selective inhibitor of glucose transporters 1 and 3 (GLUTs 1 and 3), to methods of preparing said compounds, and to the use thereof as pharmaceutically active agents, especially for the prophylaxis and/or treatment of metabolic diseases, immunological diseases, autoimmune diseases, inflammation, graft versus host disease, cancer, and metastasis thereof. Furthermore, the present invention is directed to pharmaceutical composition comprising at least one of 2,6-methanobenzo[g][1]oxacin-4-one compounds and their analog compounds.
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- Enantioselective iron/bisquinolyldiamine ligand‐catalyzed oxidative coupling reaction of 2‐naphthols
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An iron‐catalyzed asymmetric oxidative homo‐coupling of 2‐naphthols for the synthesis of 1,1′‐Bi‐2‐naphthol (BINOL) derivatives is reported. The coupling reaction provides enantioenriched BINOLs in good yields (up to 99%) and moderate enantioselectivities (up to 81:19 er) using an iron‐complex generated in situ from Fe(ClO4)2 and a bisquinolyldiamine ligand [(1R,2R)‐N1,N2‐di(quinolin‐8‐yl)cyclohexane‐1,2‐diamine, L1]. A number of ligands (L2–L8) and the analogs of L1, with various substituents and chiral backbones, were synthesized and examined in the oxidative coupling reactions.
- Liu, Wen-Bo,Usman, Muhammad,Wu, Lin-Yang
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- The Interrupted Pummerer Reaction in a Sulfoxide-Catalyzed Oxidative Coupling of 2-Naphthols
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A benzothiophene S-oxide catalyst, generated in situ by sulfur oxidation with H2O2, mediates the oxidative coupling of 2-naphthols. Key to the catalytic process is the capture and inversion of reactivity of a 2-naphthol partner, using an interrupted Pummerer reaction of an unusual benzothiophene S-oxide, followed by subsequent coupling with a second partner. The new catalytic manifold has been showcased in the synthesis of the bioactive natural products, (±)-nigerone and (±)-isonigerone. Although Pummerer reactions are used widely, their application in catalysis is rare, and our approach represents a new catalytic manifold for metal-free C?C bond formation.
- He, Zhen,Pulis, Alexander P.,Procter, David J.
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p. 7813 - 7817
(2019/05/15)
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- Double-Fold Ortho and Remote C-H Bond Activation/Borylation of BINOL: A Unified Strategy for Arylation of BINOL
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A double-fold ortho and remote C-H borylation of BINOL is described. The proposed mechanisms involved electrostatically and sterically directed ortho and remote C-H activation processes, respectively. While B2eg2 (eg = ethylene glyco
- Bisht, Ranjana,Chaturvedi, Jagriti,Pandey, Gajanan,Chattopadhyay, Buddhadeb
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supporting information
p. 6476 - 6480
(2019/08/20)
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- Efficient synthesis of 3,3'-diaryl binaphthol through a one-step method
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The invention relates to a class of catalysis reactions of binaphthol and halogenated aromatic hydrocarbons, particularly to efficient preparation of 3,3'-diaryl binaphthol and 3-Bulkyaryl binaphtholthrough a one-step method, and belongs to the technical field of asymmetric catalysis. A purpose of the present invention is to provide a simple and practical method for preparing 3,3'-diaryl binaphthol through a one-step reaction of inexpensive BINOL and a brominated aromatic hydrocarbon reagent, and is further to provide a simple and rapid method for conveniently preparing 3-aryl binaphthol withhigh steric hindrance.
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Paragraph 0041; 0078-0080; 0083; 0086; 0089; 0092
(2018/07/30)
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- Chromatographic enantioseparation by poly(biphenylylacetylene) derivatives with memory of both axial chirality and macromolecular helicity
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Novel poly(biphenylylacetylene) derivatives bearing two acetyloxy groups at the 2- and 2′-positions and an alkoxycarbonyl group at the 4′-position of the biphenyl pendants (poly-Ac's) were synthesized by the polymerization of the corresponding biphenylylacetylenes using a rhodium catalyst. The obtained stereoregular (cis-transoidal) poly-Ac's folded into a predominantly one-handed helical conformation accompanied by a preferred-handed axially twisted conformation of the biphenyl pendants through noncovalent interactions with a chiral alcohol and both the induced main-chain helicity and the pendant axial chirality were maintained, that is, memorized, after complete removal of the chiral alcohol. The stability of the helicity memory of the poly-Ac's in a solution was lower than that of the analogous poly(biphenylylacetylene)s bearing two methoxymethoxy groups at the 2- and 2′-positions of the biphenyl pendants (poly-MOM's). In the solid state, however, the helicity memory of the poly-Ac's was much more stable and showed a better chiral recognition ability toward several racemates than that of the previously reported poly-MOM when used as a chiral stationary phase for high-performance liquid chromatography. In particular, the poly-Ac-based CSP with a helicity memory efficiently separated racemic benzoin derivatives into enantiomers.
- Ishidate, Ryoma,Ikai, Tomoyuki,Kanoh, Shigeyoshi,Yashima, Eiji,Maeda, Katsuhiro
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p. 120 - 129
(2017/04/24)
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- Enantioseparation on Riboflavin Derivatives Chemically Bonded to Silica Gel as Chiral Stationary Phases for HPLC
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Acetylated and/or 3,5-dimethylphenylcarbamated riboflavins were prepared and the resulting riboflavin derivatives as well as natural riboflavin were regioselectively immobilized on silica gel through chemical bonding at the 5'-O- or 3-N-position of the riboflavin to develop novel chiral stationary phases (CSPs) for enantioseparation by high-performance liquid chromatography (HPLC). The chiral recognition abilities of the obtained CSPs were significantly dependent on the structures of the riboflavin derivatives, the position of the chemical bonding on the silica gel, and the structures of the racemic compounds. The CSPs bonded at the 5'-O-position on the silica gel tended to well separate helicene derivatives, while the CSPs bonded at the 3-N-position composed of acetylated and 3,5-dimethylphenylcarbamated riboflavins showed a better resolving ability toward helicene derivatives and bulky aromatic racemic alcohols, respectively, and some of them were completely separated into the enantiomers. The observed difference in the chiral recognition abilities of these riboflavin-based CSPs is discussed based on the difference in their structures, including the substituents of riboflavin and the positions immobilized on the silica gel. Chirality 27:507-517, 2015.
- Kumano, Daisuke,Iwahana, Soichiro,Iida, Hiroki,Shen, Chengshuo,Crassous, Jeanne,Yashima, Eiji
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p. 507 - 517
(2015/08/03)
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- Macromolecular helicity induction and memory in a poly(biphenylylacetylene) bearing an ester group and its application to a chiral stationary phase for high-performance liquid chromatography
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An optically inactive poly(biphenylylacetylene) bearing an ester group at the 4′-position of the pendants formed a preferred-handed helical conformation and biased axial chirality in the pendants through a noncovalent interaction with a chiral alcohol, both of which were retained (memorized) even after removal of the chiral alcohol. The chiral stationary phase for high-performance liquid chromatography, prepared by coating the polymer with macromolecular helicity memory on silica gel, showed good chiral recognition ability towards various racemates.
- Ishidate, Ryoma,Shimomura, Kouhei,Ikai, Tomoyuki,Kanoh, Shigeyoshi,Maeda, Katsuhiro
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p. 946 - 948
(2015/08/24)
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- MnI2-catalyzed dimerization of 2-hydroxyanthracene
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Dimerization of 2-hydroxyanthracene was investigated with 5mol% of various catalysts that are efficient catalysts for the dimerization of 2-naphthol. Catalysts such as Cu(OH)Cl TMEDA, [Mn(acac) 3], and [Mn(acac) 2] did not give satis
- Zhang, Sicheng,Wang, Yanqing,Song, Zhiyi,Nakajima, Kiyohiko,Takahashi, Tamotsu
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p. 697 - 699
(2013/07/26)
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- Divergent reaction pathways for phenol arylation by arynes: Synthesis of helicenes and 2-arylphenols
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Two reactions of phenols with arynes have been developed. If LiTMP base is employed, arynes generated from aryl chlorides react with phenols to form helicenes. o-Arylation of phenols can be achieved by employing tBuONa base in the presence of AgOAc. Direc
- Truong, Thanh,Daugulis, Olafs
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p. 531 - 535
(2013/05/08)
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- Pd(II)-catalyzed C-H activation/aryl-aryl coupling of phenol esters
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(Chemical Equation Presented) Although nitrogen-containing group-directed cyclopalladation reactions have been well-known, Pd(II) insertion into C-H bonds promoted by coordination of an oxygen-only group to the palladium remains rather rare. In the present study, the first cyclopalladation complex formed from a simple phenol ester was characterized by X-ray crystallography. A promising protocol for the ortho C-H activation/aryl-aryl coupling of phenol esters that was not sensitive to moisture or air was then established. The utility of the reaction was demonstrated for the synthesis of useful phenol derivatives. Copyright
- Xiao, Bin,Fu, Yao,Xu, Jun,Gong, Tian-Jun,Dai, Jian-Jun,Yi, Jun,Liu, Lei
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supporting information; experimental part
p. 468 - 469
(2010/03/25)
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- Enantioenriched synthesis of C 1-symmetric BINOLs: Iron-catalyzed cross-coupling of 2-naphthols and some mechanistic insight
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Highly enantioselective aerobic oxidative cross-coupling of 2-naphthols with broad substrate scope was achieved using an iron(salan) complex as the catalyst. Enantiomeric excesses of the products ranged from 87 to 95%. The scope of the cross-coupling reac
- Egami, Hiromichi,Matsumoto, Kenji,Oguma, Takuya,Kunisu, Takashi,Katsuki, Tsutomu
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supporting information; experimental part
p. 13633 - 13635
(2010/11/17)
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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; scheme or table
p. 6008 - 6014
(2010/02/28)
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- RETRACTED ARTICLE: Enantioselective organocatalytic hantzsch synthesis of polyhydroquinolines
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The four-component Hantzsch reaction provides access to pharmaceutically important dihydropyridines. To expand the utility of this method, we have developed a route under organocatalytic conditions with good yields and excellent ee's. Through catalyst scr
- Evans, Christopher G.,Gestwicki, Jason E.
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supporting information; experimental part
p. 2957 - 2959
(2009/12/05)
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- The first asymmetric halogen/metal-exchange reaction: Desymmetrization of alcohols with enantiotopic bromoarene substituents
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Desymmetrizations of the prochiral bis(bromoaryl)alcohols 1 and 4 were effected by treatment with iPr2Mg and enantiomerically pure lithium alkoxides. The resulting arylmagnesium compounds were quenched with various electrophiles. The absolute and (if relevant) relative configurations of the resulting products were determined. The best ee/yield combination was obtained for the protonolysis furnishing monobromoalcohol (R)-2 (53% ee, 51% yield). The latter was converted into (R)-orphenadrine, an antihistaminic and anticholinergic drug.
- Saelinger, Daniel,Brueckner, Reinhard
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experimental part
p. 6688 - 6703
(2010/02/28)
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- Asymmetric allylboration of aldehydes and ketones using 3,3′-disubstitutedbinaphthol-modified boronates
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Allylboronates derived from 3,3′-disubstituted 2,2′-binaphthols react with aldehydes and ketones to give the expected allylated products with up to >99:1 er. Highest selectivities were observed for aromatic ketones. The bis(trifluoromethyl) derivative is particularly outstanding in terms of reactivity, selectivity, and robustness.
- Wu, T. Robert,Shen, Lixin,Chong, J. Michael
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p. 2701 - 2704
(2007/10/03)
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- Enantioselective catalytic conjugate addition of dialkylzinc reagents using copper-phosphoramidite complexes; ligand variation and non-linear effects
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A variety of new chiral phosphoramidites was synthesised and tested in the copper-catalysed enantioselective conjugate addition of diethylzinc to cyclohexenone and chalcone in order to assess the structural features that are important for stereocontrol. A
- Arnold, Leggy A.,Imbos, Rosalinde,Mandoli, Alessandro,De Vries, André H.M.,Naasz, Robert,Feringa, Ben L.
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p. 2865 - 2878
(2007/10/03)
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- Formal total synthesis of (+)-diepoxin σ
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The highly oxygenated antifungal anticancer natural product (±)-diepoxin σ was prepared in 10 steps and in 15% overall yield from O-methylnaphthazarin. Highlights of the synthetic work include an Ullmann coupling and a possibly biomimetic oxidative spirocyclization for the introduction of the naphthalene ketal as well as the use of a retro-Diels-Alder reaction to unmask the reactive enone moiety in the naphthoquinone bisepoxide ring system. A novel highly bulky chiral binaphthol ligand was developed for a boron-mediated Diels-Alder reaction that constitutes a formal asymmetric total synthesis of (+)-diepoxin σ.
- Wipf, Peter,Jung, Jae-Kyu
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p. 6319 - 6337
(2007/10/03)
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- Synthesis and application of macrocyclic binaphthyl ligands with extended chiral bias
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Two macrocyclic and one non-cyclic chiral diphosphine ligand containing a 2,2'-bridged binaphthyl unit were synthesized in six steps from (R)-2,2'- dimethoxy-1,1'-binaphthyl in overall yields of 25 and 17%, respectively. The new ligands showed asymmetric inductions of up to 98% e.e. if used in palladium catalyzed allylic alkylation reactions.
- Yan, Yuan-Yong,Widhalm, Michael
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p. 3607 - 3610
(2007/10/03)
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- Design of bronsted acid-assisted chiral Lewis acid (BLA) catalysts for highly enantioselective Diels-Alder reactions
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Bronsted acid-assisted chiral Lewis acid (BLA) was highly effective as a chiral catalyst for the enantioselective Diels-Alder reaction of both α- substituted and α-unsubstituted α,β-enals with various dienes. Hydroxy groups in optically active binaphthol derivatives and boron reagents with electron-withdrawing substituents were used as Bronsted acids and Lewis acids, respectively. Intramolecular Bronsted acids in a chiral BLA catalyst played an important role in accelerating the rate of Diels-Alder reactions and in producing a high level of enantioselectivity. In particular, excellent enantioselectivity was achieved due to intramolecular hydrogen bonding interaction and attractive π-π donor-acceptor interaction in the transition-state assembly by hydroxy aromatic groups in a chiral BLA catalyst.
- Ishihara, Kazuaki,Kurihara, Hideki,Matsumoto, Masayuki,Yamamoto, Hisashi
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p. 6920 - 6930
(2007/10/03)
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- EXPEDIENT ROUTE TO 3- AND 3,3'-SUBSTITUTED 1,1'-BI-2-NAPHTHOLS BY DIRECTED ortho METALATION AND SUZUKI CROSS COUPLING METHODS
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A directed ortho metalation-based route to 3- and 3,3'-substituted binaphthols 2a-c and 3a-c, including chiral materials, is described.Using the Suzuki cross coupling process, dibromo system 3a (E = Br) has been transformed into 3,3'-diaryl binaphthols 5.
- Cox, Paul J.,Wang, Wei,Snieckus, Victor
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p. 2253 - 2256
(2007/10/02)
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- Host-Guest Complexation. 23. High Chiral Recognition of Amino Acid and Ester Guests by Hosts Containing One Chiral Element
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The chiral recognition properties of ten enantiomerically pure hosts toward the enantiomers of six different amino acids and their methyl esters have been examined.The hosts possessed the general structure (A)2D(OEOEO)2E, in which D is the chiral 1,1'-din
- Lingenfelter, David S.,Helgeson, Roger C.,Cram, Donald J.
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p. 393 - 406
(2007/10/02)
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