- Direct C-C bond construction from arylzinc reagents and aryl halides without external catalysts
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Direct cross-coupling between an arylzinc reagent and an aryl halide was accomplished without any external catalyst, enabling efficient and selective formation of the corresponding biaryl compound with broad functional group compatibility. Direct cross-coupling between a diarylzinc compound and an aryl iodide was accomplished without using any external catalyst. The reaction is efficient and selective, enabling formation of the corresponding biaryl compounds with broad functional group compatibility. The reaction is proposed to proceed by a thermally initiated single electron transfer (SET) route. Copyright
- Minami, Hiroki,Wang, Xuan,Wang, Chao,Uchiyama, Masanobu
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- Three-Component Difunctionalization of Cyclohexenyl Triflates: Direct Access to Versatile Cyclohexenes via Cyclohexynes
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Difunctionalization of strained cyclic alkynes presents a powerful strategy to build richly functionalized cyclic alkenes in an expedient fashion. Herein we disclose an efficient and flexible approach to achieve carbohalogenation, dicarbofunctionalization, aminohalogenation and aminocarbonation of readily available cyclohexenyl triflates. We have demonstrated the novel use of zincate base/nucleophile system for effective formation of key cyclohexyne intermediates and selective addition of various carbon and nitrogen nucleophiles. Importantly, leveraging the resulting organozincates enables the incorporation of a broad range of electrophilic partners to deliver structurally diverse cyclohexene motifs. The importance and utility of this method is also exemplified by the modularity of this approach and the ease in which even highly complex polycyclic scaffolds can be accessed in one step.
- Cho, Seoyoung,McLaren, E. J.,Wang, Qiu
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supporting information
p. 26332 - 26336
(2021/11/10)
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- FARNESOID X RECEPTOR AGONISTS AND USES THEREOF
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Described herein are compounds that are farnesoid X receptor agonists, methods of making such compounds, pharmaceutical compositions and medicaments comprising such compounds, and methods of using such compounds in the treatment of conditions, diseases, or disorders associated with farnesoid X receptor activity.
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Paragraph 00439-00440; 00487-00488
(2020/04/25)
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- Cobalt-Catalyzed α-Arylation of Substituted α-Bromo α-Fluoro β-Lactams with Diaryl Zinc Reagents: Generalization to Functionalized Bromo Derivatives
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A cobalt-catalyzed cross-coupling of α-bromo α-fluoro β-lactams with diarylzinc or diallylzinc reagents is herein disclosed. The protocol proved to be general, chemoselective and operationally simple allowing the C4 functionalization of β-lactams. The substrate scope was expanded to α-bromo lactams and amides, α-bromo lactones and esters as well as N- and O-containing heterocycles.
- Br?se, Stefan,Chen, Hi-Yung,Cossy, Janine,Koch, Vanessa,Lei, Aiwen,Lorion, Mélanie M.,Nieger, Martin
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supporting information
p. 13163 - 13169
(2020/09/23)
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- One-pot Negishi cross-coupling reaction of aryldiazonium salts via Ni catalysis induced by visible-light
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Visible-light induced catalysis is of high interest for its mild and environmentally benign properties. Herein, a general Ni catalysis accelerated by visible-light was successfully developed for one-pot Negishi coupling reactions at room temperature in a short reaction time (2Zn generated in situ from Grignard reagents and ZnBr2. This protocol provides a convenient access to C–C bond formation for important biaryl components. It tolerates various functional groups, and Hammett study illuminates the possiblility of Ni(III)/Ni(I) redox catalytic cycle.
- Wang, Lianjun,Liu, Gao
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- Quaternary Centers by Nickel-Catalyzed Cross-Coupling of Tertiary Carboxylic Acids and (Hetero)Aryl Zinc Reagents
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This work bridges a gap in the cross-coupling of aliphatic redox-active esters with aryl zinc reagents. Previously limited to primary, secondary, and specialized tertiary centers, a new protocol has been devised to enable the coupling of general tertiary systems using nickel catalysis. The scope of this operationally simple method is broad, and it can be used to simplify the synthesis of medicinally relevant motifs bearing quaternary centers.
- Chen, Tie-Gen,Zhang, Haolin,Mykhailiuk, Pavel K.,Merchant, Rohan R.,Smith, Courtney A.,Qin, Tian,Baran, Phil S.
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supporting information
p. 2454 - 2458
(2019/02/09)
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- Organic Electroluminescent Materials and Devices
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The present invention includes novel borazarophenanthrene compounds, which may be used as hosts for phosphorescent emitters, charge transporters or emitters in OLEDs.
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Paragraph 0124; 0123
(2018/03/25)
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- Iron-Catalyzed Difluoromethylation of Arylzincs with Difluoromethyl 2-Pyridyl Sulfone
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We report the first iron-catalyzed difluoromethylation of arylzincs with difluoromethyl 2-pyridyl sulfone via selective C-S bond cleavage. This method employs the readily available, bench-stable fluoroalkyl sulfone reagent and inexpensive iron catalyst, allowing facile access to structurally diverse difluoromethylated arenes at low temperatures. The experiment employing a radical clock indicates the involvement of radical species in this iron-catalyzed difluoromethylation process.
- Miao, Wenjun,Zhao, Yanchuan,Ni, Chuanfa,Gao, Bing,Zhang, Wei,Hu, Jinbo
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supporting information
p. 880 - 883
(2018/02/07)
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- Decarboxylative Negishi Coupling of Redox-Active Aliphatic Esters by Cobalt Catalysis
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A cobalt-catalyzed decarboxylative Negishi coupling reaction of redox-active aliphatic esters with organozinc reagents was developed. The method enabled efficient alkyl–aryl, alkyl–alkenyl, and alkyl–alkynyl coupling reactions under mild reaction conditions with no external ligand or additive needed. The success of an in situ activation protocol and the facile synthesis of the drug molecule (±)-preclamol highlight the synthetic potential of this method. Mechanistic studies indicated that a radical mechanism is involved.
- Liu, Xu-Ge,Zhou, Chu-Jun,Lin,Han, Xiang-Lei,Zhang, Shang-Shi,Li, Qingjiang,Wang, Honggen
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supporting information
p. 13096 - 13100
(2018/09/21)
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- Exploiting Synergistic Effects in Organozinc Chemistry for Direct Stereoselective C-Glycosylation Reactions at Room Temperature
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Pairing a range of bis(aryl) zinc reagents ZnAr2 with the stronger Lewis acidic [(ZnArF2)] (ArF=C6F5), enables highly stereoselective cross-coupling between glycosyl bromides and ZnAr2 without the use of a transition metal. Reactions occur at room temperature with excellent levels of stereoselectivity, where ZnArF2 acts as a non-coupling partner although its presence is crucial for the execution of the C(sp2)–C(sp3) bond formation process. Mechanistic studies have uncovered a unique synergistic partnership between the two zinc reagents, which circumvents the need for transition-metal catalysis or forcing reaction conditions. Key to the success of the coupling is the avoidance of solvents that act as Lewis bases versus diarylzinc compounds (e.g. THF).
- Hernán-Gómez, Alberto,Orr, Samantha A.,Uzelac, Marina,Kennedy, Alan R.,Barroso, Santiago,Jusseau, Xavier,Lemaire, Sébastien,Farina, Vittorio,Hevia, Eva
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supporting information
p. 10630 - 10634
(2018/08/01)
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- Iron catalysed Negishi cross-coupling using simple ethyl-monophosphines
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Monophosphines prepared by iron catalysed hydrophosphination have been used as pro-ligands in iron catalysed Negishi cross-coupling of alkyl bromides and diphenyl zinc reagents. The cross-coupling has been investigated with monophosphines with varying electronic properties and we find the simplest, unsubstituted phosphine to offer the optimum reaction conditions (both in terms of yield of diarylmethane product and cost-effectiveness of the phosphine). In situ catalyst generation from monophosphine and FeCl2 was used in catalysis; however, preparation of a discrete homonuclear iron complex was also achieved and this four-coordinate iron-phosphine complex was isolated and used in catalysis.
- Brown, Caleb A.,Nile, Terence A.,Mahon, Mary F.,Webster, Ruth L.
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p. 12189 - 12195
(2016/01/15)
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- Pincer-Nickel-Catalyzed Cross-Coupling of Aryl Sulfamates with Arylzinc Chlorides
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The nickel N,N,N-pincer complex 2 was demonstrated to effectively catalyze the cross-coupling of aryl sulfamates with arylzinc chlorides under mild conditions. The reaction is suitable for a wide range of substrates, and tolerates various functional groups. A nickel N,N,N-pincer complex effectively catalyzes the cross-coupling of aryl sulfamates with arylzinc chlorides under mild conditions. The reaction is suitable for a wide range of substrates, and tolerates various functional groups.
- Tao, Jian-Long,Wang, Zhong-Xia
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p. 6534 - 6540
(2015/10/19)
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- Direct C(sp2)-C(sp3) cross-coupling of diaryl zinc reagents with benzylic, primary, secondary, and tertiary alkyl halides
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The direct C(sp2)-C(sp3) cross-coupling of diaryl zinc reagents with benzylic, primary, secondary, and tertiary alkyl halides proceeded in the absence of coordinating ethereal solvents at ambient temperature without the addition of a catalyst. The C(sp2)-C(sp3) cross-coupling showed excellent functional-group tolerance, and products were isolated in high yields, generally without the requirement for purification by chromatography. This process represents an expedient, operationally simple method for the construction of new C(sp2)-C(sp3) bonds. Zinc and you'll miss it. Direct C(sp2)-C(sp3) cross-coupling of diaryl zinc reagents with alkyl halides proceeded rapidly at ambient temperature without a coordinating ethereal solvent or an added catalyst (see scheme). This versatile, operationally simple approach to C(sp2)-C(sp3) bond formation enables the expedient construction of a diverse array of carbon-based structural motifs.
- Dunsford, Jay J.,Clark, Ewan R.,Ingleson, Michael J.
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supporting information
p. 5688 - 5692
(2015/05/19)
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- On the remarkably different role of salt in the cross-coupling of arylzincs from that seen with alkylzincs
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The role of halide salt additives has been investigated in the Negishi reaction involving aryl zinc reagents. Diarylzincs readily transmetallate to Pd in relatively non-polar media (e.g., THF) with zero salt present and coupling proceeds. Arylzinc halides
- McCann, Lucas C.,Organ, Michael G.
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p. 4386 - 4389
(2014/05/06)
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- Efficient access to 3-substituted-γ-hydroxylactams: The uncatalyzed addition of diorganozinc reagents to cyclic imides with heterocyclic substitution
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A range of 3-substituted-γ-hydroxylactams have been prepared via the uncatalyzed addition of organozinc nucleophiles to cyclic imides. This reactivity is primarily limited to imides containing heterocyclic N-substitution, but proceeds efficiently with a variety of diorganozinc reagents, including those prepared and utilized without purification, as well as organozinc halides. It is hypothesized that the presence of a Lewis basic directing group is required for optimum reactivity.
- Deglopper, Kimberly S.,Dennis, Joseph M.,Johnson, Jeffrey B.
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supporting information
p. 1843 - 1845
(2014/03/21)
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- Nickel-catalyzed direct addition of diorganozinc reagents to phthalimides: Selective formation of gamma-hydroxylactams
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The nickel-catalyzed addition of diorganozinc reagents to phthalimides proceeds with excellent selectivity to provide 3-substituted-3- hydroxyisoindolin-1-one products. These 3-hydroxy-γ-lactams are produced cleanly in high yield with numerous examples of imide substitution and a broad range of diorganozinc reagents that are prepared and utilized without purification. Georg Thieme Verlag Stuttgart · New York.
- Dennis, Joseph M.,Calyore, Catherine M.,Sjoholm, Jessica S.,Lutz, J. Patrick,Gair, Joseph J.,Johnson, Jeffrey B.
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supporting information
p. 2567 - 2570
(2013/12/04)
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- Facially selective cu-catalyzed carbozincation of cyclopropenes using arylzinc reagents formed by sequential I/Mg/Zn exchange
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Described is a Cu-catalyzed directed carbozincation of cyclopropenes with organozinc reagents prepared by I/Mg/Zn exchange. This protocol broadens the scope with respect to functional group tolerance and enables use of aryl iodide precursors, rather than purified diorganozinc precursors. Critical to diastereoselectivity of the carbozincation step is the removal of magnesium halide salts after transmetalation with ZnCl2.
- Tarwade, Vinod,Selvaraj, Ramajeyam,Fox, Joseph M.
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p. 9900 - 9904
(2013/01/15)
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- PROCESS FOR THE PREPARATION OF COMPOUNDS USEFUL AS INHIBITORS OF SGLT2
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The present invention is directed to a novel process for the preparation of compounds having inhibitory activity against sodium-dependent glucose transporter (SGLT) being present in the intestine or kidney.
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Page/Page column 36
(2011/04/25)
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