- 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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- Palladium-Catalyzed Reductive Carbonylation of (Hetero) Aryl Halides and Triflates Using Cobalt Carbonyl as CO Source
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An efficient protocol for the reductive carbonylation of (hetero) aryl halides and triflates under CO gas-free conditions using Pd/Co2(CO)8 and triethylsilane has been developed. The mild reaction conditions, enhanced chemoselectivity and, easy access to heterocyclic and vinyl carboxaldehydes highlights its importance in organic synthesis.
- Dogga, Bhushanarao,Joseph, Jayan T.,Kumar, C. S. Ananda
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supporting information
p. 309 - 313
(2020/12/23)
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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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- Palladium-Catalyzed Cyclobutanation of Aryl Sulfonates through both C-O and C-H Cleavage
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A palladium-catalyzed cyclobutanation of aryl sulfonates with strained alkenes has been developed. The methodology is featured to achieve the cleavage of both C-O and C-H bonds of phenol derivatives in one pot. Under the reaction conditions, in addition t
- Zhang, Liangwei,Liu, Long,Huang, Tianzeng,Dong, Qizhi,Chen, Tieqiao,Chen, Tieqiao
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p. 2189 - 2196
(2020/06/05)
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- Practical Ni-Catalyzed Cross-Coupling of Unsaturated Zinc Pivalates with Unsaturated Nonaflates and Triflates
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A practical nickel-catalyzed cross-coupling of (hetero)aryl or alkynylzinc pivalates with various unsaturated nonaflates or triflates is described. Organozinc pivalates allow these cross-couplings to take place with high yields and a low catalyst loading (0.5 mol %). Couplings with (E)- and (Z)-alkenyl triflates proceed with retention of configuration.
- Hofmayer, Maximilian S.,Lutter, Ferdinand H.,Grokenberger, Lucie,Hammann, Jeffrey M.,Knochel, Paul
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supporting information
p. 36 - 39
(2019/01/04)
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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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- Reactions of Arylsulfonate Electrophiles with NMe4F: Mechanistic Insight, Reactivity, and Scope
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This paper describes a detailed study of the deoxyfluorination of aryl fluorosulfonates with tetramethylammonium fluoride (NMe4F) and ultimately identifies other sulfonate electrophiles that participate in this transformation. 19F NMR spectroscopic monitoring of the deoxyfluorination of aryl fluorosulfonates revealed the rapid formation of diaryl sulfates under the reaction conditions. These intermediates can proceed to fluorinated products; however, diaryl sulfate derivatives bearing electron-donating substituents react very slowly with NMe4F. Based on these findings, aryl triflate and aryl nonaflate derivatives were explored, since these cannot react to form diaryl sulfates. Aryl triflates were found to be particularly effective electrophiles for deoxyfluorination with NMe4F, and certain derivatives (i.e., those bearing electron-neutral/donating substituents) afforded higher yields than their aryl fluorosulfonate counterparts. Computational studies implicate a similar mechanism for deoxyfluorination of all the sulfonate electrophiles.
- Schimler, Sydonie D.,Froese, Robert D. J.,Bland, Douglas C.,Sanford, Melanie S.
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p. 11178 - 11190
(2018/09/12)
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- Palladium nanoparticles: Chemoselective control for reductive Heck with aryl triflates and 2,3-dihydrofuran
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The reductive-Heck reaction offers a unique entry to formal Csp2-Csp3 cross-coupling reactions that proceed in the absence of a main group organometallic coupling partner. Consequently, further development of new variants would be transformative. Unfortunately, controlling the relative rates of the organopalladium intermediates has proven difficult with homogenous, single-site Pd catalysts. This work describes a selective reductive Heck reaction catalyzed by Pd-nanoparticles. The reaction works well with electron-deficient aryl triflates at room temperature in the absence of ligands. This work addresses some of the challenges found in the reductive-Heck literature.
- Rosas Vargas, Daisy,Cook, Silas P.
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supporting information
p. 3314 - 3317
(2018/05/04)
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- A simple route to 1,4-addition reactions by Co-catalyzed reductive coupling of organic tosylates and triflates with activated alkenes
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An efficient Co-catalyzed 1,4-addition reaction of alkyl/aryl triflates and tosylates with activated alkenes is described. In this reaction, an air-stable cobalt(ii) complex, a mild reducing agent Zn and a simple proton source (H2O) are used. A radical mechanism for the addition of alkyl tosylates to activated alkenes is likely involved.
- Hsieh, Jen-Chieh,Chu, Yi-Hua,Muralirajan, Krishnamoorthy,Cheng, Chien-Hong
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supporting information
p. 11584 - 11587
(2017/10/27)
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- Copper-Catalyzed C-S Bond Formation via the Cleavage of C-O Bonds in the Presence of S8 as the Sulfur Source
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Useful and applicable methods for one-pot and odorless synthesis of unsymmetrical and symmetrical diaryl sulfides via C-O bond activation are presented. First, a new efficient procedure for the synthesis of unsymmetrical sulfides using the cross-coupling reaction of phenolic esters such as acetates, tosylates, and triflates and with arylboronic acid or triphenyltin chloride as the coupling partners is reported. Depending on the reaction, S 8 /KF or S 8 /NaO t -Bu system is found to be an effective source of sulfur in the presence of copper salts and in poly(ethylene glycol) as a green solvent. Then, the synthesis of symmetrical diaryl sulfides from phenolic compounds by using S 8 as the sulfur source and NaO t -Bu in anhydrous DMF at 120 °C under N 2 is described. By these protocols, the synthesis of a variety of unsymmetrical and symmetrical sulfides become easier than the available protocols in which thiols and aryl halides are directly used for the preparation of the sulfides.
- Rostami, Abed,Rostami, Amin,Ghaderi, Arash,Gholinejad, Mohammad,Gheisarzadeh, Sajedeh
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p. 5025 - 5038
(2017/10/06)
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- A Nickel-Catalyzed Carbonyl-Heck Reaction
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The use of transition-metal catalysis to enable the coupling of readily available organic molecules has greatly enhanced the ability of chemists to access complex chemical structures. In this work, an intermolecular coupling reaction that unites organotriflates and aldehydes is presented. A unique catalyst system is identified to enable this reaction, featuring a Ni0 precatalyst, a tridentate Triphos ligand, and a bulky amine base. This transformation provides access to a variety of ketone-containing products without the selectivity- and reactivity-related challenges associated with more traditional Friedel–Crafts reactions. A Heck-type mechanism is postulated, wherein the π bond of the aldehyde takes the role of the olefin in the insertion/elimination steps.
- Vandavasi, Jaya Kishore,Hua, XiYe,Halima, Hamdi Ben,Newman, Stephen G.
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supporting information
p. 15441 - 15445
(2017/11/10)
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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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- Scope of direct arylation of fluorinated aromatics with aryl sulfonates
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The scope and limitations of direct arylation of fluorinated aromatics with aryl sulfonates was examined. Pd(OAc)2, in the presence of MePhos and KOAc in THF, efficiently catalyzed the direct arylation of fluoro aromatics with aryl triflates un
- Chang, Joyce Wei Wei,Chia, Eugene Yurong,Chai, Christina Li Lin,Seayad, Jayasree
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supporting information; experimental part
p. 2289 - 2299
(2012/04/10)
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- Direct synthesis of primary arylamines via C-N cross-coupling of aryl bromides and triflates with amides
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Aryl halides and triflates are coupled with primary amides to give the corresponding arylamines in the presence of a palladium catalyst, a suitable ligand, and a base. The catalyst system performs well for a large number of different substrates at 100-150 °C without solvent, and with low catalyst levels (0.12 mol % Pd). Nicotinamide might be useful as a nitrogen source in the Pd-catalyzed amination reaction.
- Romero,Harrak,Basset,Orúe,Pujol
-
experimental part
p. 1951 - 1956
(2009/07/11)
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- Generation and suppression of 3-/4-functionalized benzynes using zinc ate base (TMP-Zn-ate): New approaches to multisubstituted benzenes
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We present full details of our new methods for preparing functionalized benzynes with lithium di-alkyl(2,2,6,6-tetramethylpiperidino)zincate (R 2Zn(TMP)Li) through deprotonative zincation as a key reaction. In this system, by choosing appropriate ligands for the zincate, either regioselective zincation of functionalized haloaromatics or the generation of substituted benzynes can be controlled in good yields with excellent chemoselectivity, using the same substrate. Zincation with tBu 2Zn(TMP)Li followed by electrophilic trapping or zincation with Me2Zn(TMP)Li followed by nucleophilic or diene trapping is shown to be a powerful tool for the chemoselective preparation of 1,2,3-/1,2,4- trisubstituted benzene derivatives. These methods offer far greater generality than previous methods for the synthesis of multifunctionalized benzenes. Computational/theoretical studies of the reaction mechanism of this unique benzyne formation indicated that preferential coordination of the dialkylzinc moiety of zincate to halogen is the reason for the reduced activation energy of the elimination, that is, for the formation of the benzyne. The role of the ligands on Zn in accelerating/decelerating the elimination is also discussed.
- Uchiyama, Masanobu,Kobayashi, Yuri,Furuyama, Taniyuki,Nakamura, Shinji,Kajihara, Yumiko,Miyoshi, Tomoko,Sakamoto, Takao,Kondo, Yoshinori,Morokuma, Keiji
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p. 472 - 480
(2008/10/09)
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- Heterogeneous Pd/C-catalyzed ligand-free, room-temperature suzuki-miyaura coupling reactions in aqueous media
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A mild and efficient ligand-free Suzuki-Miyaura coupling reaction catalyzed by heterogeneous Pd/C was developed. Aryl bromides and triflates undergo the cross-coupling with aryl boronic acids in excellent yields without the presence of any additives in aqueous media at room temperature. Aryl vinyl boronic acids are also applicable to this coupling reaction and provide the trans-stilbene derivatives in high yields. The application of wet-type Pd/C to the coupling reaction was achieved without any loss of activity under aerobic conditions, and the reuse of Pd/C is feasible for a fifth run without significant loss of activity. Inductively coupled plasma (ICP) mass-spectrometric analysis of the filtrate from the reaction mixture of 4-bromonitrobenzene with phenylboronic acid demonstrated that the palladium metal hardly leached into the solution within the limits of the detector ( 1 ppm), thus suggesting that the present Suzuki-Miyaura reaction proceeded by heterogeneous catalysis.
- Maegawa, Tomohiro,Kitamura, Yoshiaki,Sako, Satoko,Udzu, Takahiro,Sakurai, Ai,Tanaka, Asami,Kobayashi, Yusuke,Endo, Koichi,Bora, Utpal,Kurita, Takanori,Kozaki, Atsushi,Monguchi, Yasunari,Sajiki, Hironao
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p. 5937 - 5943
(2008/02/13)
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- 2,2′-bipyridine: An efficient ligand in the cobalt-catalyzed synthesis of organozinc reagents from aryl chlorides and sulfonates
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The synthesis of functionalized arylzinc reagents from aromatic chlorides, triflates, or mesylates, via cobalt catalysis, is reported using 2,2′-bipyridine as a ligand in a mixture of acetonitrile and pyridine. This procedure allows the synthesis of a variety of functionalized arylzinc species in good to excellent yields. Some of these arylzinc compounds have been coupled with aromatic bromides under palladium catalysis. Georg Thieme Verlag Stuttgart.
- Kazmierski, Igor,Gosmini, Corinne,Paris, Jean-Marc,Périchon, Jacques
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p. 881 - 884
(2007/10/03)
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- Zinc trimethylsilylamide as a mild ammonia equivalent and base for the amination of aryl halides and triflates
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(Chemical Equation Presented) We report that Zn[N(SiMe3) 2]2 is a mild ammonia equivalent and base for the palladium-catalyzed amination of aryl halides and triflates. In contrast to LiN(SiMe3)2, the combination of Zn[N(SiMe 3)2]2 and LiCl coupled with aryl halides and triflates containing base-sensitive functionality in high yields. In addition, aryl bromides coupled with aryl and alkylamines with the combination of Zn[N(SiMe3)2]2 and LiCl as base. These aminations occurred without racemization of the enolizable stereocenter of an optically active ester.
- Lee, Dae-Yon,Hartwig, John F.
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p. 1169 - 1172
(2007/10/03)
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- Preparation and Palladium-Catalyzed Cross-Coupling of Aryl Triethylammonium Bis(catechol) Silicates with Aryl Triflates
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Pentavalent aryl and heteroaryl bis(catechol) silicates undergo palladium-catalyzed cross-coupling with aryl and heteroaryl triflates in the presence of a fluoride source in excellent yields. These solid, air-stable bis(catechol) silicates are prepared from a high-yielding displacement reaction between catechol and an aryl siloxane in the presence of an amine base. The cross-coupling reaction is tolerant of a wide range of electron-donating and electron-withdrawing groups. Several examples of di-ortho-substituted triflates are successfully coupled with these reagents.
- Seganish, W. Michael,DeShong, Philip
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p. 1137 - 1143
(2007/10/03)
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- A complementary method to obtain N-acyl enamides using the Heck reaction: Extending the substrate scope for asymmetric hydrogenation
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A series of N-acyl enamides were prepared using the Heck reaction. Asymmetric hydrogenation provided protected amines in up to 99% ee. A method to prepare N-acyl enamides is reported that is complementary to the existing protocols. Heck reaction of a vari
- Harrison, Paul,Meek, Graham
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p. 9277 - 9280
(2007/10/03)
-
- Palladium-catalyzed phosphination of functionalized aryl triflates
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Catalytic user-friendly approach to the syntheses of various functionalized aromatic phosphines from their corresponding substituted aryl triflates and triarylphosphines was accomplished. This method is carried out in neutral media and compatible with man
- Kwong, Fuk Yee,Lai, Chi Wai,Yu, Michael,Tian, Yuan,Chan, Kin Shing
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p. 10295 - 10305
(2007/10/03)
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- Fast Synthesis of Aryl Triflates with Controlled Microwave Heating
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matrix presented Synthesis of aryl triflates from phenols using N-phenyltriflimide requires only 6 min for completion when conducted with controlled microwave heating. The methodology was applied to both solution- and solid-phase conditions. Ten different
- Bengtson, Anna,Hallberg, Anders,Larhed, Mats
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p. 1231 - 1233
(2007/10/03)
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- A soluble polymer-supported triflating reagent: a high-throughput synthetic approach to aryl and enol triflates.
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[reaction: see text] The high-yielding synthesis and application of the first example of a polymer-supported reagent for the preparation of trifluoromethanesulfonates (triflates) is described. This new reagent efficiently triflates aryl alcohols and lithi
- Wentworth,Wentworth Jr.,Mansoor,Janda
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p. 477 - 480
(2007/10/03)
-
- A facile route to aryl amines: Nucleophilic substitution of aryl triflates
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The aromatic nucleophilic substitution (S(N)Ar) between aryl triflates and secondary amines has been studied. In the absence of solvent, the reaction proceeds at room temperature for nitro and cyano activated aryl triflates and requires higher temperatures in the case of carboxy activation. Variable triflate reactivity could be explained in terms of frontier molecular orbital theory. This methodology has been applied for the synthesis of substituted piperidyl pyridines.
- Schio, Laurent,Lemoine, Guy,Klich, Michel
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p. 1559 - 1562
(2007/10/03)
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- New platelet fibrinogen receptor glycoprotein IIb-IIIa antagonists: Orally active series of N-alkylated amidines with a 6,6-bicyclic template
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The design, synthesis, and pharmacological evaluation of (S)-(-)-ethyl [6-[4-(morpholino-formimidoyl)benzamido]-3,4-dihydro-2H-1-benzopyran-3- yl]acetate hydrochloride ((S)-4·HCl, MS-180), an orally active glycoprotein IIb-IIIa (GPIIb-IIIa) antagonist, are reported. Pharmacophore mapping of amidino and carboxyl groups of already known GPIIb-IIIa antagonists led to the synthesis of nine amidino acids containing 6,6-bicyclic ring skeletons (10a-i). Among them, the compounds 10a,c,e having an amide bond and 1,2,3,4- tetrahydronaphthalene or 3,4-dihydro-2H-1-benzopyran skeleton showed marked inhibitions with IC50 values of 46-57 nM in human platelet aggregation assay in vitro, but low oral activities. N-Alkylation of the amidino group coupled with the ester prodrug approach afforded MS-180 ((S)-4·HCl), which generates in vivo the corresponding carboxylic acid (S)-3 as an active species. In vitro, (S)-3 inhibited ADP-induced aggregation of guinea pig, dog, and human platelets (IC50 = 110, 253, and 35 nM, respectively) and inhibited the binding of fibrinogen to immobilized GPIIb-IIIa of human platelets (IC50 = 0.12 nM). After oral administration of MS-180 ((S)4·HCl) to fasted beagle dog, ex vivo inhibition of platelet aggregation was observed. The maximal inhibitions were observed 2-4 h after dosing with dose dependency (60% inhibition at a dose of 1 mg/kg, 85% at 3 mg/kg, and 100% at 10 mg/kg, respectively) and the extent of the inhibitions paralleled the plasma concentration of the active species (S)-3. On the basis of these studies, we selected MS-180 ((S)-4·HCl) as a candidate for clinical evaluation as a drug for the treatment and prevention of thrombosis in patients.
- Okumura, Kunio,Shimazaki, Toshiyuki,Aoki, Yoji,Yamashita, Hiroyuki,Tanaka, Eishi,Banba, Shinichi,Yazawa, Kouhei,Kibayashi, Kenji,Banno, Hitoshi
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p. 4036 - 4052
(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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- High pressure organic chemistry; XI. A new convenient synthesis of aromatic amines from activated phenols
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Aryl triflates containing electron-withdrawing substituents efficiently react with amines in refluxing acetonitrile or at 10 kbar pressure to give various aromatic amines.
- Kotsuki,Kobayashi,Suenaga,Nishizawa
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p. 1145 - 1147
(2007/10/02)
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- Palladium Catalysed Alkoxycarbonylation of Phenols to Benzoate Esters
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The methoxycarbonylation of aryl trifluoromethanesulphonates with CO and aliphatic alcohols is catalysed by Pd(OAc)2-1,3-bis(diphenylphosphino)propane in high yield at 70 deg C and ambient CO pressure.
- Dolle, Roland E.,Schmidt, Stanley J.,Kruse, Lawrence I.
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p. 904 - 905
(2007/10/02)
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