15106-88-4Relevant academic research and scientific papers
Atom-efficient transition-metal-free arylation ofN,O-acetals using diarylzinc reagents through Zn/Zn cooperativity
Borys, Andryj M.,Gil-Negrete, Jose M.,Hevia, Eva
supporting information, p. 8905 - 8908 (2021/09/10)
Exploiting the cooperative action of Lewis acid Zn(C6F5)2with diarylzinc reagents, the efficient arylation ofN,O-acetals to access diarylmethylamines is reported. Reactions take place under mild reaction conditions without the need for transtion-metal catalysis. Mechanistic investigations have revealed that Zn(C6F5)2not only acts as a Lewis acid activator, but also enables the regeneration of nucleophilic ZnAr2species, allowing a limiting 50 mol% to be employed.
Mixed Alkyl/Aryl Diphos Ligands for Iron-Catalyzed Negishi and Kumada Cross Coupling Towards the Synthesis of Diarylmethane
Ma, Xufeng,Wang, Han,Liu, Yao,Zhao, Xing,Zhang, Jun
, p. 5134 - 5140 (2021/11/16)
Mixed alkyl/aryl diphos ligands have been prepared and their application in iron-catalyzed cross coupling of benzylic chlorides with diaryl zinc (Negishi) or aryl Grignard reagents (Kumada) towards the synthesis of diarylmethane has been evaluated. The iron?diphos catalytic system exhibited the enhanced activity and selectivity in the two coupling reactions. The electron-rich mixed PPh2/PCy2 ligands outperformed their symmetrical PPh2 congeners, and led to decreased homocoupling byproduct formation. It indicates that the electronic effect of the ligands plays an important role in the catalytic performance. The Fe catalyst supported by L8 bearing an electron-rich PCy2 substituent and a sterically demanding tert-butyl on ethene backbone exhibited the best catalytic performance and good functional group tolerance in the two cross coupling reactions.
Three-Component Difunctionalization of Cyclohexenyl Triflates: Direct Access to Versatile Cyclohexenes via Cyclohexynes
Cho, Seoyoung,McLaren, E. J.,Wang, Qiu
supporting information, p. 26332 - 26336 (2021/11/10)
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.
SALT, ACID GENERATOR, RESIST COMPOSITION, AND METHOD FOR PRODUCING RESIST PATTERN
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Paragraph 0220, (2020/12/01)
PROBLEM TO BE SOLVED: To provide a salt and a resist composition capable of producing a resist pattern with good CD uniformity (CDU). SOLUTION: A salt represented by formula (I), an acid generator, and a resist composition containing the same are provided. [R1, R2, R3, R4, R5 and R6 each represent a halogen atom or the like; R7 and R8 each represent a halogen atom, OH or the like; R9 represents H or an alkyl group; m7 and m8 each represent an integer of 0-2; m9 represents an integer of 0-5; Q1 and Q2 each represent F or a perfluoroalkyl group; L1 represents a substituted/unsubstituted saturated hydrocarbon group; and Y1 represents a substituted/unsubstituted methyl group or alicyclic hydrocarbon group.] SELECTED DRAWING: None COPYRIGHT: (C)2021,JPO&INPIT
Cobalt-Catalyzed α-Arylation of Substituted α-Bromo α-Fluoro β-Lactams with Diaryl Zinc Reagents: Generalization to Functionalized Bromo Derivatives
Br?se, Stefan,Chen, Hi-Yung,Cossy, Janine,Koch, Vanessa,Lei, Aiwen,Lorion, Mélanie M.,Nieger, Martin
supporting information, p. 13163 - 13169 (2020/09/23)
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.
Quaternary Centers by Nickel-Catalyzed Cross-Coupling of Tertiary Carboxylic Acids and (Hetero)Aryl Zinc Reagents
Chen, Tie-Gen,Zhang, Haolin,Mykhailiuk, Pavel K.,Merchant, Rohan R.,Smith, Courtney A.,Qin, Tian,Baran, Phil S.
supporting information, p. 2454 - 2458 (2019/02/09)
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.
Chiral Lithium Amido Aryl Zincates: Simple and Efficient Chemo- and Enantio-Selective Aryl Transfer Reagents
Chaumont-Olive, Pauline,Rouen, Mathieu,Barozzino-Consiglio, Gabriella,Ben Abdeladhim, Amel,Maddaluno, Jacques,Harrison-Marchand, Anne
supporting information, p. 3193 - 3197 (2019/01/25)
An enantioselective aryl transfer is promoted using chiral tricoordinated lithium amido aryl zincates that are easily accessible reagents and whose chiral appendage is simply recovered for reuse. The arylation reaction is run in good yields (60 % average on twenty substrates) and high enantiomeric excesses (95 % ee average). This occurs whatever the ortho, meta, or para substituent borne by the substrate and a complete chemoselectivity is observed with respect to the aldehyde function. Sensitive groups such as nitriles, esters, ketones, and enolisable substrates resist to the action of the ate reagent, warranting a large scope to this methodology.
Decarboxylative Negishi Coupling of Redox-Active Aliphatic Esters by Cobalt Catalysis
Liu, Xu-Ge,Zhou, Chu-Jun,Lin,Han, Xiang-Lei,Zhang, Shang-Shi,Li, Qingjiang,Wang, Honggen
supporting information, p. 13096 - 13100 (2018/09/21)
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.
Iron-Catalyzed Difluoromethylation of Arylzincs with Difluoromethyl 2-Pyridyl Sulfone
Miao, Wenjun,Zhao, Yanchuan,Ni, Chuanfa,Gao, Bing,Zhang, Wei,Hu, Jinbo
supporting information, p. 880 - 883 (2018/02/07)
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.
Exploiting Synergistic Effects in Organozinc Chemistry for Direct Stereoselective C-Glycosylation Reactions at Room Temperature
Hernán-Gómez, Alberto,Orr, Samantha A.,Uzelac, Marina,Kennedy, Alan R.,Barroso, Santiago,Jusseau, Xavier,Lemaire, Sébastien,Farina, Vittorio,Hevia, Eva
supporting information, p. 10630 - 10634 (2018/08/01)
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).
