- On the preparation of ortho-trifluoromethyl phenyl triflate
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In contrast to an earlier report advocating a copper-mediated trifluoromethylation of ortho-iodophenyl triflate, ortho-trifluoromethyl phenyl triflate may be prepared simply by reacting the corresponding phenol with triflic anhydride in the presence of a
- Gill, Duncan,Hester, Alison J.,Lloyd-Jones, Guy C.
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- Ni-Catalyzed Cross-Electrophile Coupling of Aryl Triflates with Thiocarbonates via C-O/C-O Bond Cleavage
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A nickel-catalyzed reductive coupling of aryl triflates with thiocarbonates is reported here. Both electron-rich and -deficient aryl C(sp2)-O electrophiles as well as a class of O-tBu S-alkyl thiocarbonates are compatible with the optimized reaction conditions, as evidenced by 49 examples. The reaction also proceeds with good chemoselective cleavage of the C-O bond with regard to thioesters. This work broadens the scope of nickel-catalyzed reductive cross-electrophile coupling reactions.
- Zhu, Zhaodong,Gong, Yuxin,Tong, Weiqi,Xue, Weichao,Gong, Hegui
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supporting information
p. 2158 - 2163
(2021/04/05)
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- Bismuth-Catalyzed Oxidative Coupling of Arylboronic Acids with Triflate and Nonaflate Salts
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Herein we present a Bi-catalyzed cross-coupling of arylboronic acids with perfluoroalkyl sulfonate salts based on a Bi(III)/Bi(V) redox cycle. An electron-deficient sulfone ligand proved to be key for the successful implementation of this protocol, which allows the unusual construction of C(sp2)-O bonds using commercially available NaOTf and KONf as coupling partners. Preliminary mechanistic studies as well as theoretical investigations reveal the intermediacy of a highly electrophilic Bi(V) species, which rapidly eliminates phenyl triflate.
- Cornella, Josep,Peciukenas, Vytautas,Planas, Oriol
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supporting information
p. 11382 - 11387
(2020/07/14)
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- Base-promoted selective O-phosphorylation of aryl triflates with P(O)-H compounds
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Compared to previous transition metal-catalyzed C-phosphorylation reactions for constructing C–P bonds, in the absence of transition metal catalysts and ligands, a direct O-phosphorylation of aryl triflates selectively occurred with P(O)-H compounds in the presence of a base via the construction of O–P bonds. This transformation proceeds under simple and mild conditions, and provides a new method for the preparation of valuable organophosphoryl compounds from readily available P(O)-H compounds and triflates.
- Wang, Mingyue,Yang, Jia,Wang, Shuai,Zhong, Hong
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supporting information
(2020/05/05)
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- Solvent-free ruthenium-catalysed triflate coupling as a convenient method for selective azole-o-C-H monoarylation
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Metal-catalysed ortho-directed C-H functionalization usually faces selectivity issues in the competition between mono- and disubstitution processes. We report herein the ruthenium-catalysed N-directed C-H monoarylation of arylpyrazoles with a selectivity
- Abidi, Oumaima,Boubaker, Taoufik,Hierso, Jean-Cyrille,Roger, Julien
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supporting information
p. 5916 - 5919
(2019/06/24)
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- Palladium-Catalyzed Chemoselective Negishi Cross-Coupling of Bis[(pinacolato)boryl]methylzinc Halides with Aryl (Pseudo)Halides
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We describe a palladium-catalyzed chemoselective Negishi cross-coupling of a bis[(pinacolato)boryl]methylzinc halide with aryl (pseudo)halides. This reaction affords an array of benzylic 1,1-diboronate esters, which can serve as useful synthetic handles f
- Lee, Hyojae,Lee, Yeosan,Cho, Seung Hwan
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supporting information
p. 5912 - 5916
(2019/08/20)
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- Enantioselective Construction of Tertiary Boronic Esters by Conjunctive Cross-Coupling
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Catalytic enantioselective conjunctive cross-coupling has been developed to construct tertiary alkylboronic esters. These reactions occur with good yield and enantioselectivity for a range of substrates. Mechanistic experiments reveal aspects of the catalytic cycle that allow hindered substrates to react without significant complicating side reactions.
- Myhill, Jesse A.,Zhang, Liang,Lovinger, Gabriel J.,Morken, James P.
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supporting information
p. 12799 - 12803
(2018/09/14)
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- A Stereoselective Reductive Hosomi-Sakurai Reaction
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A novel reductive variant of the classical Hosomi-Sakurai reaction is reported. This transformation hinges on a redox-neutral, stereoselective internal reduction event under mild conditions. This operationally simple reaction relies on readily available starting materials and leads to useful products in diastereoselectivities of up to 7:1. The versatility of this new method is demonstrated through the stereoselective one-step synthesis of an AChE inhibitor.
- Bauer, Adriano,Maulide, Nuno
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supporting information
p. 1461 - 1464
(2018/03/09)
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- Pd-Catalyzed Conjunctive Cross-Coupling between Grignard-Derived Boron “Ate” Complexes and C(sp2) Halides or Triflates: NaOTf as a Grignard Activator and Halide Scavenger
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Catalytic enantioselective conjunctive cross-couplings that employ Grignard reagents are shown to furnish an array of nonracemic chiral organoboronic esters in an efficient and highly selective fashion. The utility of sodium triflate in facilitating this reaction is two-fold: it enables “ate” complex formation and overcomes catalytic inhibition by halide ions.
- Lovinger, Gabriel J.,Aparece, Mark D.,Morken, James P.
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supporting information
p. 3153 - 3160
(2017/03/11)
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- Enantioselective Conjunctive Cross-Coupling of Bis(alkenyl)borates: A General Synthesis of Chiral Allylboron Reagents
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Palladium-catalyzed conjunctive cross-coupling is used for the synthesis of enantioenriched allylboron reagents. This reaction employs nonsymmetric bis(alkenyl)borates as substrates and appears to occur by a mechanism that involves selective activation of the less substituted alkene followed by migration of the more substituted alkene during the course of a Pd-induced metalate rearrangement.
- Edelstein, Emma K.,Namirembe, Sheila,Morken, James P.
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supporting information
p. 5027 - 5030
(2017/05/04)
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- Nickel-Catalyzed Cyanation of Aryl Chlorides and Triflates Using Butyronitrile: Merging Retro-hydrocyanation with Cross-Coupling
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We describe a nickel-catalyzed cyanation reaction of aryl (pseudo)halides that employs butyronitrile as a cyanating reagent instead of highly toxic cyanide salts. A dual catalytic cycle merging retro-hydrocyanation and cross-coupling enables the conversion of a broad array of aryl chlorides and aryl/vinyl triflates into their corresponding nitriles. This new reaction provides a strategically distinct approach to the safe preparation of aryl cyanides, which are essential compounds in agrochemistry and medicinal chemistry.
- Yu, Peng,Morandi, Bill
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supporting information
p. 15693 - 15697
(2017/12/02)
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- Oxidative Addition of Aryl Electrophiles to a Prototypical Nickel(0) Complex: Mechanism and Structure/Reactivity Relationships
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Detailed kinetic studies of the reaction of a model Ni0 complex with a range of aryl electrophiles have been conducted. The reactions proceed via a fast ligand exchange pre-equilibrium, followed by oxidative addition to produce either [NiIX(dppf)] (and biaryl) or [NiII(Ar)X(dppf)]; the ortho substituent of the aryl halide determines selectivity between these possibilities. A reactivity scale is presented in which a range of substrates is quantitatively ranked in order of the rate at which they undergo oxidative addition. The rate of oxidative addition is loosely correlated to conversion in prototypical cross-coupling reactions. Substrates that lead to NiI products in kinetic experiments produce more homocoupling products under catalytic conditions.
- Bajo, Sonia,Laidlaw, Gillian,Kennedy, Alan R.,Sproules, Stephen,Nelson, David J.
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supporting information
p. 1662 - 1672
(2017/04/28)
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- AZEPANYL-DERIVATIVES AND PHARMACEUTICAL COMPOSITIONS COMPRISING THE SAME WITH ANTIPARASITIC ACTIVITY
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The present invention provides compounds of Formula (i). Furthermore, pharmaceutical compositions are provided comprising at least one compound of Formula (i), for the treatment of parasitic diseases including malaria, as well as neurodegenerative diseases.
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Page/Page column 77
(2016/01/25)
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- Nickel-catalyzed phosphorylation of aryl triflates with P([Formula presented] compounds
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A nickel-catalyzed phosphorylation of aryl triflates with P([Formula presented] compounds is disclosed. This reaction can proceed smoothly under a mild reaction condition, producing the corresponding aryl phosphorus compounds in good to high yields.
- Yang, Jia,Xiao, Jing,Chen, Tieqiao,Han, Li-Biao
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p. 120 - 124
(2016/08/23)
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- PIPERIDINYLCARBAZOLE AS ANTIMALARIAL
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The present invention provides compounds of Formula (I) for the treatment of parasitic diseases including malaria, as well as neurodegenerative diseases. Formula (I) wherein R3, R4, X and Y have the meaning given in claim 1.
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Page/Page column 85
(2014/07/23)
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- Highly active catalysts of bisphosphine oxides for asymmetric Heck reaction
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Bisphosphine oxides formed highly active asymmetric Heck catalysts, which were applied in asymmetric synthesis of pharmacologically active azacycles. Olefin insertion proceeded via cis pathways, different from P,N-ligands.
- Hu, Jian,Lu, Yunpeng,Li, Yongxin,Zhou, Jianrong
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supporting information
p. 9425 - 9427
(2013/10/01)
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- Achieving vinylic selectivity in Mizoroki-heck reaction of cyclic olefins
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In Heck reactions of cyclic olefins, the products usually have aryl groups that end up at the allylic and/or homoallylic position. We herein report new selectivity that adds aryl groups to the vinylic position. Cyclic olefins of various ring size worked well. The desired isomers were produced by palladium-hydride-catalyzed isomerization of the initial products. Thus, a specific catalyst must be used so that it can perform two jobs under one set of reaction conditions. Copyright
- Wu, Xiaojin,Lu, Yunpeng,Hirao, Hajime,Zhou, Jianrong
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supporting information
p. 6014 - 6020
(2013/06/26)
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- Nickel-catalyzed C-H/C-O coupling of azoles with phenol derivatives
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The first nickel-catalyzed C-H bond arylation of azoles with phenol derivatives is described. The new Ni(cod)2/dcype catalytic system is active for the coupling of various phenol derivatives such as esters, carbamates, carbonates, sulfamates, triflates, tosylates, and mesylates. With this C-H/C-O biaryl coupling, we synthesized a series of privileged 2-arylazoles, including biologically active alkaloids. Moreover, we demonstrated the utility of the present reaction for functionalizing estrone and quinine.
- Muto, Kei,Yamaguchi, Junichiro,Itami, Kenichiro
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supporting information; experimental part
p. 169 - 172
(2012/03/07)
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- Regioselectivity switch achieved in the palladium catalyzed α-arylation of enones by employing the modified Kuwajima-Urabe conditions
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A new regioselective approach to the synthesis of α-aryl enones is reported. This represents an important application of the Kuwajima-Urabe protocol toward the synthesis of this simple albeit complex functional array. Several α-aryl enones were synthesized by the palladium catalyzed arylation of triethylsilylenol ethers of enones with high regioselectivity and broad scope, utilizing sterically encumbered electron-rich phosphine ligands to drive the reaction.
- Kale, Ajit Prabhakar,Pawar, Govind Goroba,Kapur, Manmohan
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supporting information; experimental part
p. 1808 - 1811
(2012/06/18)
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- Mechanistic study of a Pd/C-catalyzed reduction of aryl sulfonates using the Mg-MeOH-NH4OAc system
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A method for the deoxygenation of phenolic hydroxy groups via aryl triflates or mesylates has been established by using a combination of Pd/ C-Mg-MeOH. The addition of NH4OAc to the system markedly accelerated the reaction rate and expanded the scope of the reaction. Mechanistic studies suggested that a single-electron transfer process from the Pd0 center to the benzene ring is involved in the reduction of aryl sulfonates and that NH4OAc works as a solubilization re agent of the Mg salt and as an accelerator of the electron transfer, thus enhancing the reaction process. Our method was also applicable to the regioselective deuteration of benzene derivatives with CH3OD as the solvent and deuterium source: the original hydroxy group could be efficiently replaced with a deuterium atom.
- Mori, Akinori,Mizusaki, Tomoteru,Ikawa, Takashi,Maegawa, Tomohiro,Monguchi, Yasunari,Sajiki, Hironao
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p. 1432 - 1441
(2008/02/04)
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- Cross-coupling reaction of organostannanes with aryl halides catalyzed by nickeltriphenylphosphine or nickel-lithium halide complex
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A nickel(0) complex used in combination with lithium bromide was found to enhance the rate of the cross-coupling reaction of aryl halides with organostannanes, whereas a Ni(0) catalyst combined with Ph3P was applicable to a wide variety of aryl halides including aryl chlorides.
- Shirakawa, Eiji,Yamasaki, Kenji,Hiyama, Tamejiro
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p. 1544 - 1549
(2007/10/03)
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- First synthesis of ortho-trifluoromethylated aryl triflates
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An efficient method for the preparation of trifluoromethylated aryl triflates (trifluoromethanesulfonates) has been developed. Treatment of 2-iodophenol with trifluoromethanesulfonic anhydride in the presence of triethylamine gives triflate 3. Then, reaction of compound 3 with FSO2CF2CO2Me and CuI in DMF-HMPA affords trifluoromethylated aryl triflate 2. This reaction sequence is also successful for meta- and para-trifluoromethylated aryl triflates. Based on this methodology, the trifluoromethylated aryl triflate 11, a key intermediate for the preparation of the conformationally restricted retinoid 8 containing a trifluoromethyl group, has been synthesized. The cross-coupling of aryl triflate 11 with vinylstannane 17 under palladium catalysis provides compound 18, the methyl ester of retinoid 8, in moderate yield.
- Qing, Feng-Ling,Fan, Junfa,Sun, Hong-Bin,Yue, Xiang-Jun
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p. 3053 - 3057
(2007/10/03)
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- Nickel- and Palladium-Catalyzed Homocoupling of Aryl Triflates. Scope, Limitation, and Mechanistic Aspects
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Whereas the direct reduction of aryl triflates affords mainly phenols and some arenes, the presence of a catalytic amount of palladium or nickel results in the formation of biaryls. The homocoupling is performed in the presence of an electron source, either a cathode or zinc powder. A judicious choice of the metal (nickel or palladium), the ligand (monodentate or bidentate phosphine), and the reduction process (electrochemical or chemical) allows the synthesis of functional symmetrical biaryls. Nickel and palladium complexes ligated by bidentate ligands such as NiCl2(dppf) and Pd(OAc)2 + 1 BINAP are very efficient for the homocoupling of 1-naphthyl triflate, since the dimer was obtained in almost quantitative yield. However, the homocoupling is sensitive to steric hindrance, excluding for the moment the synthesis of atropisomers. The homocoupling proceeds via an activation of the C - O bond of the aryl triflate by a palladium(0) (or a nickel(0)) complex, providing an intermediate arylpalladium(II) (or nickel(II)) complex that after activation by electron transfer affords a new complex able to undergo a second oxidative addition with the aryl triflates.
- Jutand, Anny,Mosleh, Adil
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p. 261 - 274
(2007/10/03)
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