- Chiral Selenide/Achiral Sulfonic Acid Cocatalyzed Atroposelective Sulfenylation of Biaryl Phenols via a Desymmetrization/Kinetic Resolution Sequence
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Enantioselective synthesis of axially chiral sulfur-containing biaryl derivatives through the electrophilic sulfenylation of biaryl phenols has been achieved for the first time. This catalytic asymmetric system, which involves sequential desymmetrization and kinetic resolution, is enabled by a combination of a novel 3,3′-disubstituted BINOL-derived selenide catalyst and an achiral sulfonic acid. Control experiments and computational studies suggest that multiple noncovalent interactions between the cocatalysts and substrate, especially a network of hydrogen bond interactions, play a crucial role in determining the enantioselectivity and reactivity.
- Luo, Hui-Yun,Li, Zi-Hao,Zhu, Deng,Yang, Qin,Cao, Ren-Fei,Ding, Tong-Mei,Chen, Zhi-Min
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supporting information
p. 2943 - 2952
(2022/02/23)
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- Oxidation of BINOLs by Hypervalent Iodine Reagents: Facile Synthesis of Xanthenes and Lactones
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Xanthene derivatives have broad applications in medicines, fluorescent probes, dyes, food additives, etc. Therefore, much attention was focused on developing the synthetic methods to prepare these compounds. Binaphthyl-based xanthene derivatives were prepared through the oxidation of BINOLs promoted by the hypervalent iodine reagent iodosylbenzene (PhIO). Nine-membered lactones were obtained through a similar oxidative reaction when iodoxybenzene (PhIO2) was used. Additionally, one-pot reactions of BINOLs, PhIO and nucleophiles such as alcohols and amines were also investigated to provide alkoxylated products and amides in good to excellent yields.
- Wirth, Thomas,Zhang, Huaiyuan
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- An enantioselective oxidative coupling reaction of 2-naphthol derivatives catalyzed by chiral diphosphine oxide-iron(ii) complexes
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An enantioselective oxidative coupling of 2-naphthol derivatives is developed with the use of chiral Fe(ii)-diphosphine oxide complexes. Optically active 1,1-bi-2-naphthol derivatives can be synthesized in high yields when a 2?:?1 complex of (S)-xylyl-iPrO-BIPHEP-oxide and Fe(OTf)2 is used in the presence of t-butyl hydroperoxide as an oxidant. The non-linear effect, X-ray crystal structure and ESI-MS suggest that a 2?:?1 complex of (S)-xylyl-iPrO-BIPHEP-oxide and Fe(OTf)2 is a pre-catalyst for a Fe(iii)/Fe(iv) redox cycle.
- Horibe, Takahiro,Nakagawa, Keita,Hazeyama, Takashi,Takeda, Kazuki,Ishihara, Kazuaki
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supporting information
p. 13677 - 13680
(2019/11/19)
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- Enantioselective vinylation of aldehydes with the vinyl Grignard reagent catalyzed by magnesium complex of chiral BINOLs
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Enantioselective vinylation of aldehydes via direct catalytic asymmetric Grignard reaction of aldehdyes and the vinyl Grinard reagent is a long-standing challenge. This work demonstrated that the magnesium (S)-3,3′-dimethyl BINOLate enantioselectively catalyze the direct vinylation of aldehydes with the deactivated vinylmagnesium bromide by bis(2-[N,N′-dimethylamino]ethyl) ether (BDMAEE) in the addition of n-butylmagnesium chloride. The highest ee of 63% was achieved up to date.
- Wang, Pei,Ma, Guo-Rong,Yu, Sheng-Li,Da, Chao-Shan
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supporting information
p. 79 - 86
(2018/12/13)
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- Enantioselective Vanadium-Catalyzed Oxidative Coupling: Development and Mechanistic Insights
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The evolution of a more reactive chiral vanadium catalyst for enantioselective oxidative coupling of phenols is reported, ultimately resulting in a simple monomeric vanadium species combined with a Br?nsted or Lewis acid additive. The resultant vanadium complex is found to effect the asymmetric oxidative ortho-ortho coupling of simple phenols and 2-hydroxycarbazoles with good to excellent levels of enantioselectivity. Experimental and quantum mechanical studies of the mechanism indicate that the additives aggregate the vanadium monomers. In addition, a singlet to triplet crossover is implicated prior to carbon-carbon bond formation. The two lowest energy diastereomeric transition states leading to the enantiomeric products differ substantially with the path to the minor enantiomer involving greater torsional strain between the two phenol moieties.
- Kang, Houng,Herling, Madison R.,Niederer, Kyle A.,Lee, Young Eun,Vasu Govardhana Reddy, Peddiahgari,Dey, Sangeeta,Allen, Scott E.,Sung, Paul,Hewitt, Kirsten,Torruellas, Carilyn,Kim, Gina J.,Kozlowski, Marisa C.
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p. 14362 - 14384
(2018/11/23)
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- Direct asymmetric reductive amination for the synthesis of (S)-rivastigmine
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In this article we demonstrate how asymmetric total synthesis of (S)-rivastigmine has been achieved using direct asymmetric reductive amination as the key transformation in four steps. The route started with readily available and cheap m-hydroxyacetophenone, through esterification, asymmetric reductive amination, N-diphenylmethyl deprotection and reductive amination, to provide the final (S)-rivastigmine in 82% overall yield and 96% enantioselectivity. In the asymmetric reductive amination, catalysed by the iridium–phosphoramidite ligand complex and helped by some additives, the readily prepared 3-acetylphenyl ethyl(methyl)carbamate directly reductively coupled with diphenylmethanamine to yield the chiral amine product in 96% ee and 93% yield.
- Gao, Guorui,Du, Shaozhi,Yang, Yang,Lei, Xue,Huang, Haizhou,Chang, Mingxin
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supporting information
(2018/09/10)
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- Photochemical Oxidative Coupling of 2-Naphthols using a Hybrid Reduced Graphene Oxide/Manganese Dioxide Nanocomposite under Visible-Light Irradiation
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We describe a simple, cost-effective, efficient, and high-yielding photocatalytic approach for the oxidative self-dimerization of 2-naphthols using a semiconductor–metal hybrid that consists of intercalated manganese dioxide nanoparticles in reduced graphene oxide (rGO/MnO2) under visible-light irradiation. The desired photocatalyst was synthesized in a single step by mixing MnO2 nanoparticles with rGO ultrasonically. The hybrid photocatalyst exhibited a significantly higher activity than neat MnO2 nanoparticles and rGO, which is believed to be because of the synergistic effect of its components. To our knowledge, this hybrid rGO/MnO2 nanocomposite is the first heterogeneous, green photocatalyst for the oxidative coupling of 2-naphthols under mild conditions.
- Kumar, Anurag,Aathira,Pal, Ujjwal,Jain, Suman L.
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p. 1844 - 1852
(2018/02/12)
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- Tuning ligand structure in chiral bis(phosphite) and mixed phosphite-phosphinite PCP-palladium pincer complexes
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A range of chiral resorcinol bis(phosphite) and phosphite-phosphinite ligands were produced and their propensity to form palladium PCP-pincer complexes examined. The ease of base-assisted C-H palladation of the ligands falls in the order bis(phosphinite)
- Bedford, Robin B.,Chang, Yu-Ning,Haddow, Mairi F.,McMullin, Claire L.
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scheme or table
p. 9034 - 9041
(2011/10/30)
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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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- Highly catalytic asymmetric addition of deactivated alkyl Grignard reagents to aldehydes
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[Chemical Equation Presented] Generally used and highly reactive RMgBr reagents were effectively deactivated by bis[2-(N,N-dimethylamino)ethyl] ether and then were employed in the highly enantioselective addition of Grignard reagents to aldehydes. The reaction was catalyzed by the complex of commercially available (S)-BINOL and Ti(O'-Pr)4 under mild conditions. Compared with the other observed Grignard reagents, alkyl Grignard reagents showed higher enantioselectivity and they achieved >99% ee.
- Da, Chao-Shan,Wang, Jun-Rul,Yin, Xiao-Gang,Fan, Xin-Yuan,Liu, Yi,Yu, Sheng-Li
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supporting information; experimental part
p. 5578 - 5581
(2010/03/02)
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- Copper-catalyzed enantioselective conjugate addition of Grignard reagents to acyclic enones using monodentate phosphoramidite ligands
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Herein, we report efficient catalysts based on phosphoramidites for the asymmetric copper-catalyzed conjugate addition of Grignard reagents to acyclic α,β-unsaturated ketones. A variety of Grignard reagents can be added to aliphatic and aromatic acyclic e
- Maciá, Beatriz,Fernández-Ibá?ez, M. ángeles,Mr?i?, Nata?a,Minnaard, Adriaan J.,Feringa, Ben L.
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p. 1877 - 1880
(2008/09/18)
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- A mechanistic investigation of the asymmetric Meerwein-Schmidt-Ponndorf- Verley reduction catalyzed by BINOL/AlMe3 - Structure, kinetics, and enantioselectivity
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(Chemical Equation Presented) The kinetics of the Al-catalyzed asymmetric Meerwein-Schmidt-Ponndorf-Verley (MSPV) reduction are presented. Structural identification of the catalytic precursor formed in situ between (S)-2,2′-dihydroxy-1,1′-binapthyl ((S)-BINOL), AlMe3, and 2-propanol was established through 1H and 27Al NMR spectroscopies, and APCIMS. All experimental evidence points toward the formation of a BINOL-chelated, pentacoordinate aluminum species in solution. Ligand-accelerated catalysis was confirmed for the phenolate/AlMe 3/2-propanol system. The rate law for the catalytic reaction was determined to be nearly unimolecular dependent on aluminum, zero-order dependent on substrate, and inversely dependent on 2-propanol. At the low catalyst loading employed in the BINOL/AlMe3 system, the inherent reversibility of the MSPV reaction does not affect product yield or enantiomeric excess over time. Systematic ligand studies imply that while a tetrahedral geometry around the aluminum center may result in the most active MSPV reduction catalysts, the enantioselectivity of the reaction is enhanced when the aluminum center allows for a 2-point coordination of the substrate to achieve a pentacoordinate geometry with the fifth ligand weakly coordinated to the axial site of a pseudo square pyramid.
- Graves, Christopher R.,Zhou, Hongying,Stern, Charlotte L.,Nguyen, SonBinh T.
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p. 9121 - 9133
(2008/03/27)
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- Binaphthol-based diphosphite ligands in asymmetric nickel-catalyzed hydrocyanation of styrene and 1,3-cyclohexadiene: Influence of steric properties
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A series of chiral (R)-binaphthol-based diphosphite ligands with different substituents was prepared and applied in the asymmetric nickel-catalyzed hydrocyanation of styrene and 1,3-cyclohexadiene to investigate the influence of their steric properties. The optimum steric properties for the hydrocyanation reaction lie within a narrow window. With the optimized ligand, hydrocyanation of styrene gave full conversion (Subs/Ni = 100) with 49% ee, the TON was determined to be 600. Hydrocyanation of 1,3-cyclohexadiene gave 50% conversion (Subs/Ni = 500) with an excellent ee of 86 %. This demonstrates that high ees are not only accessible for vinylarenes but also for conjugated dienes in the asymmetric nickelcatalyzed hydrocyanation.
- Wilting, Jos,Janssen, Michele,Mueller, Christian,Lutz, Martin,Spek, Anthony L.,Vogt, Dieter
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p. 350 - 356
(2008/02/07)
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- Ruthenium(II) complexes of monodonor ligands: Efficient reagents for asymmetric ketone hydrogenation
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A series of BINOL-derived ligands have been prepared and incorporated into ruthenium(II) complexes containing a diamine ligand. The complexes have proven to be excellent catalysts for the asymmetric hydrogenation of ketones, giving reduction products with enantiomeric excesses of up to 99%.
- Xu, Yingjian,Clarkson, Guy C.,Docherty, Gordon,North, Carl L.,Woodward, Gary,Wills, Martin
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p. 8079 - 8087
(2007/10/03)
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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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- Compositions and methods for selectively binding amines or amino acid enantiomers over their counter-enantiomers
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Naphthyl crown ether ligand molecules containing at least two naphthyl groups that are covalently bonded to suitable solid supports and coated by hydrophobic organic solvents are disclosed. These compositions and associated methods are characterized by selectivity of desired amine or amino acid enantiomers over their counter-enantiomers and derivatives. The composition preferably has an α-value greater than or equal to 4. This allows for the separation of such enantiomers with nonchromatographic resin bed separations of three separation stages or less.
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Page column 15; 16
(2010/11/30)
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- Microwave-assisted efficient oxidative coupling of 2-naphthols in the solid state
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Microwave-assisted oxidative coupling of 2-naphthols at solid state gave the corresponding coupling products in high yields, which provides a simple, rapid and efficient approach to the preparation of binaphthols.
- Ji, Shun-Jun,Lu, Jianmei,Zhu, Xinlin,Yang, Jin,Lang, Jian-Ping,Wu, Lin
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p. 3069 - 3074
(2007/10/03)
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- HPLC enantioseparation with cellulose tris(3,5-dichlorophenylcarbamate) in aqueous methanol as a mobile phase
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The appropriate design of mobile and stationary phase combinations allowed the use of cellulose tris(3,5-dichlorophenylcarbamate) (CDCPC) as the chiral stationary phase (CSP) in high-performance liquid chromatography (HPLC). Together with previous data obtained in n-hexane/2-propanol as a mobile phase the present study indicates very high chiral resolving ability of CDCPC.
- Chankvetadze, Bezhan,Yamamoto, Chiyo,Okamoto, Yoshio
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p. 352 - 353
(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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- Enantioselective synthesis of binaphthol derivatives by oxidative coupling of naphthol derivatives catalyzed by chiral diamine-copper complexes
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A highly efficient process of aerobic oxidative coupling of 2-naphthol derivatives catalyzed by 1 mol % of Cu(OH)Cl·TMEDA has been developed. Enantioselective oxidative coupling of naphthols was achieved by the use of 10 mol % of chiral catalysts prepared from proline-derived diamines and cuprous chloride, affording the corresponding binaphthols in good enantioselectivities of up to 78% ee. The ester moiety at the 3-position of the substrate was found to be essential for the good asymmetric induction observed in the present coupling reaction.
- Nakajima, Makoto,Miyoshi, Irie,Kanayama, Kumiko,Hashimoto, Shun-Ichi,Noji, Masahiro,Koga, Kenji
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p. 2264 - 2271
(2007/10/03)
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- Enantiopure 3-amido or 3,3′-bisamido substituted 1,1′-bi-2-naphthols by anionic Fries rearrangements
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Mono- or di-carbamates of 1,1′-bi-2-naphthol ortholithiate with BusLi-TMEDA. The resulting anions may either be captured by MeI or allowed to undergo anionic Fries rearrangement. Thus generalised two-step routes to mono- and di-(3-alkyl) or -(3-amido) substituted 2,2′-binapthols is demonstrated.
- Dennis, Mike R.,Woodward, Simon
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p. 1081 - 1085
(2007/10/03)
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- Aerobic oxidative coupling of 2-naphthoi derivatives catalyzed by a copper-amine complex without solvent
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Aerobic oxidative coupling of naphthols catalyzed by a copper-amine complex was found to proceed without solvent in high efficacy. The present reaction was applied to a practical synthesis of l,l'-binaphthalene-2,2'-dio] on multi-gram scale.
- Nakajima, Makoto,Hashimoto, Shun-Ichi,Noji, Masahiro,Koga, Kenji
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p. 1814 - 1815
(2007/10/03)
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- A New Catalytic System for Aerobic Oxidative Coupling of 2-Naphthol Derivatives by the Use of CuCl-Amine Complex: A Practical Synthesis of Binaphthol Derivatives
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Aerobic oxidative coupling of 2-naphthol derivatives by the use of 1 molpercent of CuCl-amine complex afforded binaphthol derivatives in excellent yields.
- Noji, Masahiro,Nakajima, Makoto,Koga, Kenji
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p. 7983 - 7984
(2007/10/02)
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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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- The oxidative cross-coupling of substituted 2-naphthols. Part I: The scope and limitations
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Highly selective oxidative cross-coupling of differently substituted 2-naphthols mediated by Cu(II)-tert-butyl amine complexes is described. The 'cross'-products are obtained in good to excellent yields and the selectivity up to >90% is observed depending on the substitution of naphthol nuclei. The alternative procedures - the cross-coupling of free naphthols with CuCl(OMe) as well as the coupling of sodium naphtholates with anhydrous copper(II) chloride - were also studied. All these methods enable a simple and high-yield access to the unsymmetrically substituted binaphthols. A successful optical resolution of methyl 2,2'-dihydroxy-1,1'-binaphthalene-3-carboxylate by means of liquid chromatography on triacetylcellulose and the subsequent configurational correlation with a binaphthol derivative of known absolute configuration is reported.
- Hovorka,Scigel,Gunterova,Tichy,Zavada
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p. 9503 - 9516
(2007/10/02)
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- HIGHLY SELECTIVE OXIDATIVE CROSS-COUPLING OF SUBSTITUTED 2-NAPHTHOLS: A CONVIENT APPROACH TO UNSYMMETRICAL 1,1'-BINAPHTHALENE-2,2'-DIOLS
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Oxidative cross-coupling of several differently substituted 2-naphthols mediated by Cu(II)-amine complexes is described.The influence of substituents was examined and possible mechanism explaining the observed selectivity has been proposed.
- Hovorka, Martin,Guenterova, Jana,Zavada, Jiri
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p. 413 - 416
(2007/10/02)
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- Lithiumaluminium hydride compounds
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Lithium 1,1'-binaphthyl-2,2'-dioxyaluminium hydride compounds of the general formula: STR1 wherein R1 represents a hydrogen atom, or a methyl or ethyl group, and R2 represents a straight- or branched-chain alkyl group containing from 1 to 12 carbon atoms unsubstituted or substituted by at least one fluorine atom, hydroxy group, or straight- or branched-chain alkoxy group containing from 1 to 4 carbon atoms, or represents a phenyl group unsubstituted or substituted by at least one straight- or branched-chain alkyl group containing from 1 to 4 carbon atoms are useful as reducing agents.
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- Host- Guest Complexation. 22. Reciprocal Chiral Recognition between Amino Acids and Dilocular Systems
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The direction of configurational bias and the extent of chiral recognition have been determined for complexation between seven amino acid perchlorate guests and four macrocyclic polyether hosts containing chiral elements.In solution experiments, racemic g
- Peacock, Stephen S.,Walba, David M.,Gaeta, Fred C. A.,Helgeson, Roger C.,Cram, Donald J.
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p. 2043 - 2052
(2007/10/02)
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