- A one-pot two-step synthesis of tertiary alcohols combining the biocatalytic laccase/TEMPO oxidation system with organolithium reagents in aerobic aqueous media at room temperature
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The one-pot/two-step combination of enzymes and polar organometallic chemistry in aqueous media is for the first time presented as a proof-of-concept study. The unprecedented combination of the catalytic oxidation of secondary alcohols by the system laccase/TEMPO with the ultrafast addition (3 s reaction time) of polar organometallic reagents (RLi/RMgX) to thein situformed ketones, run under air at room temperature, allows the straightforward and chemoselective synthesis of tertiary alcohols with broad substrate scope and excellent conversions (up to 96%).
- Capriati, Vito,Cicco, Luciana,García-álvarez, Joaquín,González-Sabín, Javier,Lecuna, Ramón,Presa Soto, Alejandro,Ríos-Lombardía, Nicolás,Ramos-Martín, Marina,Vitale, Paola
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supporting information
p. 13534 - 13537
(2021/12/23)
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- Catalytic Enantioselective Arylation and Heteroarylation of Ketones with Organotitanium Reagents Generated In Situ
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A practical and useful, catalytic enantioselective method has been developed for the synthesis of tertiary diaryl and aryl heteroaryl carbinols starting from commercially available aromatic ketones and aryl or heteroaryl bromides. In this method, organotitanium reagents are generated in situ from the bromides by lithiation with nBuLi followed by transmetallation of the resulting organolithiums with ClTi(OiPr)3. Treatment of the ketones with the titanium reagents in the presence of (R)-3-(3,5-bistrifluoromehthylphenyl)-1,1′-bi-2-naphthol (BTFP-BINOL) affords the corresponding tertiary alcohols in high enantioselectivities and yields. The reaction can also start with furan and 2-thienyllithium. The method is operationally simple and can be conducted on a 10-mmol scale without any difficulties.
- Matsuda, Atsushi,Ushimaru, Tomoya,Kobayashi, Yusuke,Harada, Toshiro
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p. 8605 - 8609
(2017/06/30)
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- Scandium(III) Trifluoromethanesulfonate Catalyzed Selective Reactions of Donor–Acceptor Cyclopropanes with 1,1-Diphenylethanols: An Approach to Polysubstituted Olefins
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An unexpected synthetic approach to polysubstituted olefins through the scandium(III) trifluoromethanesulfonate catalyzed ring-opening reaction of donor–acceptor cyclopropanes with 1,1-diphenylethanols was developed. The reactions, which are experimentally easy to handle, feature tolerance of various functional groups and mild reaction conditions. On the basis of experimental evidence, a plausible mechanism was also proposed.
- Zhu, Xiaoyan,Hong, Gang,Hu, Chen,Wu, Shengying,Wang, Limin
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supporting information
p. 1547 - 1551
(2017/04/01)
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- Compound used as Bruton tyrosine kinase inhibitor, and preparation method and application of compound
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The invention provides a compound with a structure shown as the formula (I), or an isomer, pharmaceutically acceptable solvate and salt thereof, which is used as the Bruton tyrosine kinase inhibitor. The Bruton tyrosine kinase inhibitor has higher inhibit
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Paragraph 0290; 0291; 0292; 0293
(2017/08/29)
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- BTK INHIBITORS
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Provided are Bruton's Tyrosine Kinase (Btk) inhibitor compounds according to Formula I, or pharmaceutically acceptable salts thereof, or pharmaceutical compositions comprising these compounds and their use in therapy. In particular, provided is the use of Btk inhibitor compounds of Formula I in the treatment of Btk mediated disorders.
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Page/Page column 112
(2016/07/27)
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- Conducting moisture sensitive reactions under mechanochemical conditions
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Dry organic solvents are used for various organic reactions that employ moisture sensitive reagents. The processes to dry these solvents are hazardous and costly. Setting up reactions in an open atmosphere while using moisture sensitive reagents has little to no effect on the rate or yield of the reaction under mechanochemical conditions. We believe this is partly due to the gaseous nature of the water vapor in the air compared to the dissolved water and oxygen in solution.
- Waddell, Daniel C.,Clark, Tammara D.,MacK, James
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body text
p. 4510 - 4513
(2012/10/07)
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- Highly enantioselective arylation of aldehydes and ketones using AlArEt2(THF) as aryl sources
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A series of AlArEt2(THF) (Ar = Ph (la), 4-MeC6H 4 (1b), 4-MeOC6H 4 (1c), 4-Me 3SiC6H4 (1d), 2-naphthyl (le)) were synthesized from reactions of AlEt2Br(THF) with ArMgBr. In CDC13 solution, the 1H NMR spectra showed that AlArEt2(THF) compounds exist as a mixture of four species of formulas of AlAr xEt3-x (THF) (x = 0, 1, 2, or 3). AlArEt2(THF) compounds were found to be superior and atom-economic reagents for asymmetric aryl additions to organic carbonyls. Aryl additions of AlArEt2(THF) to aldehydes catalyzed by the titanium(IV) complex of (R)-H8-BINOL were efficient with a short reaction time of 1 h, affording aryl addition products as exclusive or main products in high yields and excellent enantioselectivities of up to 98% ee. Although ethyl additions to aldehydes occurred in minor extent, this study demonstrates that increasing the amount of AlArEt2(THF) from 1.2 to 1.4 or to 1.6 equiv significantly improved the aryl addition products of up to >99%. On the other hand, asymmetric arylations of AlArEt2(THF) to ketones employing a titanium(IV) catalyst of (S)-BINOL produced optically active tertiary alcohols exclusively in excellent enantioselectivities of up to 94% ee.
- Zhou, Shuangliu,Wu, Kuo-Hui,Chen, Chien-An,Gau, Han-Mou
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supporting information; experimental part
p. 3500 - 3505
(2009/09/30)
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- 4,5-DIHYDRO-OXAZOL-2-YL AMINE DERIVATIVES
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The present invention relates to a compounds of formula I wherein R1, R1′, R2, R3, R4, X, Ar, and m are as defined in the specification and claims and pharmaceutically active acid addition salts thereof. Compounds of the invention have Asp2 (β-secretase, BACE 1 or Memapsin-2) inhibitory activity and are useful for the treatment of diseases characterized by elevated β-amyloid levels or β-amyloid deposits, particularly Alzheimer's disease.
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Page/Page column 12-13
(2009/09/05)
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- Gold(I)-catalyzed oxidative cleavage of a C-C double bond in water
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Oxidative cleavage of the C=C bond to afford ketone or aldehyde products with tert-butyl hydrogenperoxide (TBHP) as the oxidant can be catalyzed by AuCl with neocuproine (1) in water.
- Xing, Dong,Guan, Bingtao,Cai, Guixin,Fang, Zhao,Yang, Liping,Shi, Zhangjie
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p. 693 - 696
(2007/10/03)
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- Charge-transfer interactions in 4-donor 4′-acceptor substituted 1,1-diphenylethenes
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Two 1,1-diphenylethenes bearing either a 4-dimethylamino or 4-methoxy group as electron donor and a 4′-cyano group as electron acceptor, as well as compounds containing only a donor or acceptor functionality, were synthesized. The observation of strong fl
- Van Walree, Cornelis A.,Kaats-Richters, Veronica E. M.,Veen, Sandra J.,Wieczorek, Birgit,Van Der Wiel, Johanna H.,Van Der Wiel, Bas C.
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p. 3046 - 3056
(2007/10/03)
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- Preparation of 1,1-diphenylethanols by addition of organotitanium compounds to substituted aceto- and benzophenones
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The 1,1-diphenylethanols 5a-h were prepared by the addition of phenyltitanium triisopropoxide (3) to 4-substituted acetophenones 1a-h. The titanium tetraalkoxide 7, formed in situ from 3 and 1a, forms complexes with up to two molecules of 1a, this was established by 13C-NMR. Preparation of the alcohols 5a-f was also carried out by the reaction of methyltitanium triisopropoxide (4) with 4-substituted benzophenones 2a-f.
- Dimitrov,Stanchev,Milenkov,Nikiforov,Demirev
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p. 228 - 232
(2007/10/02)
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