- Nickel-Catalyzed Arylation/Alkenylation of tert-Cyclobutanols with Aryl/Alkenyl Triflates via a C - C Bond Cleavage
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Herein, we first present a nickel-catalyzed arylation and alkenylation of tert-cyclobutanols with aryl/alkenyl triflates via a C-C bond cleavage. An array of γ-substituted ketones was obtained in moderate-to-good yields, thus featuring earth-abundant nick
- Wang, Zhen,Hu, Yuanyuan,Jin, Hongwei,Liu, Yunkui,Zhou, Bingwei
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p. 466 - 474
(2020/12/22)
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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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- Palladium-Catalyzed Synthesis of N, N-Dimethylanilines via Buchwald-Hartwig Amination of (Hetero)aryl Triflates
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This work delineates the synthesis of N,N-dimethylaniline derivatives from dimethylamines and aryl triflates. The palladium-catalyzed C-N bond formation proceeds in excellent yields, using an unsophisticated catalytic system, a mild base, and triflates as electrophiles, which are readily available from inexpensive phenols. N,N-Dimethylanilines are multifunctional reaction partners and represent useful but underutilized building blocks in organic synthesis.
- Pospech, Jola,Taeufer, Tobias
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p. 7097 - 7111
(2020/06/27)
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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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- 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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- 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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- The Directed ortho Metalation (D o M)-Cross-Coupling Connection: Synthesis of Polyfunctional Biaryls
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A comparative evaluation of the combined directed ortho metalation (D o M)-Suzuki-Miyaura and D o M-Negishi cross-coupling reactions with aryl triflates for the synthesis of substituted biaryls is described. Both ortho -zinc and ortho -boron aryl directed
- Quesnelle, Claude A.,Snieckus, Victor
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supporting information
p. 4413 - 4428
(2018/11/21)
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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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- 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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- 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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- Selective arylation and vinylation at the α position of vinylarenes
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In intermolecular Heck reactions of styrene and vinylarenes, the aryl and vinyl groups routinely insert at the β position. However, selective insertion at the α position has been very rare. Herein, we provide a missing piece in the palette of Heck reaction, which gave >20:1 α selectivity. The key to our success is a new ferrocene 1,1′-bisphosphane (dnpf) that carries 1-naphthyl groups. Our mechanistic studies revealed that the high α selectivity is partly attributable to the steric effect of dnpf. The rigid and bulky 1-naphthyl groups of dnpf sterically disfavor β insertion. What the Heck! In intermolecular Heck reactions, insertion at the β position of aromatic olefins is very common, but reversal of the selectivity for selective α insertion has been a longstanding problem. A general method to couple aryl and vinyl triflates with aromatic olefins in >20:1 α selectivity is presented. The key to this successful approach is a new ferrocene bisphosphane with naphthyl groups on the phosphorus atom (see scheme; OTf=triflate). Copyright
- Zou, Yinjun,Qin, Liena,Ren, Xinfeng,Lu, Yunpeng,Li, Yongxin,Zhou, Jianrong
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supporting information
p. 3504 - 3511
(2013/07/05)
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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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- CHIRAL PHOSPHINES FOR PALLADIUM-CATALYZED ASYMMETRIC ALPHA-ARYLATION OF ESTER ENOLATES TO PRODUCE TERTIARY STEREOCENTERS IN HIGH ENANTIOSELECTIVITY
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The disclosure provides new and improved methods for the Pd-catalyzed asymmetric α-arylation of ester compounds, which produce the corresponding α-aryl moiety in high enantioselectivity (generally >90% ee). The present methods utilize a palladium catalyst supported by new (R)-H8-BINOL-derived monophosphine ligands. The method is applicable to a wide variety of aryl triflate substrates having variations in both electronic and steric properties. These aryl triflate substrates react with various α-alkyl (Z)- and/or (E)-0-trimethylsilyl ketene acetals in the presence of a Pd catalyst, (R)-H8-BINOL-derived monophosphine ligand, and a mild activator, for example, LiOAC, to provide the asymmetric α-arylation of ester compounds in high ee.
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Paragraph 00160-00161
(2013/03/26)
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- Intermolecular mizoroki-heck reaction of aliphatic olefins with high selectivity for substitution at the internal position
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New ligand for old reaction: The title reaction of aryltriflates with aliphatic olefins leads to substitution at the internal position with high selectivity. The ratio of the desired isomer (shown in the scheme) to the sum of all other isomers is generall
- Qin, Liena,Ren, Xinfeng,Lu, Yunpeng,Li, Yongxin,Zhou, Jianrong
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supporting information; experimental part
p. 5915 - 5919
(2012/07/30)
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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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- 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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- An enantioselective, intermolecular α-arylation of ester enolates to form tertiary stereocenters
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In transition-metal catalyzed, asymmetric α-arylation of carbonyl compounds, formation of tertiary centers with high enantioselectivity is a longstanding problem, due to easy enolization of the monoarylation products. Herein, we report such examples using a palladium catalyst supported by a new, (R)-H8-BINOL-derived monophosphine. Silyl ketene acetals, together with a weakly basic activator, were used as equivalents of ester anions, and they reacted smoothly with aryl triflates in excellent enantiomeric excess (ee). The usefulness of the reaction was demonstrated in a gram-scale synthesis of (S)-Naproxen in 92% ee.
- Huang, Zhiyan,Liu, Zheng,Zhou, Jianrong
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supporting information; experimental part
p. 15882 - 15885
(2011/11/13)
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- Low-Temperature Ag/Pd-catalyzed decarboxylative cross-coupling of aryl trflates with aromatic carboxylate salts
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Chemical Equation Presented At 50°C lower than the best known copper catalysts, a catalytic silver(I)/ palladium(II) system allows the decarboxylative cross-coupling of arenecarboxylates with aryl triflates at temper-atures as low as 120°C. Remarkably, polychlorinated and many heterocyclic arenecarboxylates are converted for the first time in high yields. FG = functional group.
- Goossen, Lukas J.,Lange, Paul P.,Rodriguez, Nuria,Linder, Christophe
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supporting information; experimental part
p. 3906 - 3909
(2010/07/03)
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- Biaryl and aryl ketone synthesis via Pd-catalyzed decarboxylase coupling of carboxylate salts with aryl triflates
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A bimetallic catalyst system has been developed that for the first time allows the decarboxylative crosscoupling of aryl and acyl carboxylates with aryl triflates. In contrast to aryl halides, these electrophiles give rise to non-coordinating anions as byproducts, which do not interfere with the decarboxylation step that leads to the generation of the carbon nucleophilic crosscoupling partner. As a result, the scope of carboxylate substrates usable in this transformation was extended from ortho-substituted or otherwise activated derivatives to a broad range of ortho-, meta-, and para-substituted aromatic carboxylates. Two alternative protocols have been optimized, one involving heating the substrates in the presence of CuI/1,10- phenanthroline (10-15 mol %) and PdI2/phosphine (23 mol%) in NMP for 1-24 h, the other involving CuI/l,10-phenanthroline (615mol%) and PdBr2/Tol-BINAP (2 mol % ) in NMP using microwave heating for 5-10 min. While most products are accessible using standard heating, the use of microwave irradiation was found to be beneficial especially for the conversion of non-activated carboxylates with functionalized aryl triflates. The synthetic utility of the transformation is demonstrated with 48 examples showing the scope and limitations of both protocols. In mechanistic studies, the special role of microwave irradiation is elucidated, and further perspectives of decarboxylase crosscouplings are discussed.
- Goossen, Lukas J.,Linder, Christophe,Rodriguez, Nuria,Lange, Paul P.
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supporting information; experimental part
p. 9336 - 9349
(2010/04/03)
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- Decarboxylative biaryl synthesis from aromatic carboxylates and aryl triflates
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A new catalyst system, generated in situ from Cu2O, 1,10-phenanthroline, PdI2, and Tol-BINAP, for the first time allows the decarboxylative coupling of carboxylic acids with aryl triflates. In contrast to previous decarboxylative couplings that remained limited to certain activated carboxylates, e.g., ortho-substituted benzoates, this halide-free protocol is generally applicable to aromatic carboxylic acid salts regardless of their substitution pattern. Copyright
- Goossen, Lukas J.,Rodriguez, Nuria,Linder, Christophe
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supporting information; experimental part
p. 15248 - 15249
(2009/03/11)
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- One-pot synthetic procedure for 2,2′-disubstituted biaryls via the Suzuki coupling reaction of aryl triflates in a biphasic solvent system
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A one-pot synthetic procedure for 2,2′-disubstituted biaryls was developed via a Suzuki cross-coupling reaction of aryl triflates in a biphasic solvent system. The effects of various bases and solvents were investigated. Results showed that the Na2/
- Miura, Masanori,Koike, Takanori,Ishihara, Tsukasa,Hirayama, Fukushi,Sakamoto, Shuichi,Okada, Minoru,Ohta, Mitsuaki,Tsukamoto, Shin-Ichi
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p. 3809 - 3820
(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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- Fluorodediazoniation in ionic liquid solvents: New life for the Balz-Schiemann reaction
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Drawbacks associated with the classic Balz-Schiemann reaction are eliminated in a series of examples by conducting fluorodediazoniation in ionic liquid solvents, thus opening up a new horizon for a much in demand process.
- Laali, Kenneth K.,Gettwert, Volker J.
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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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- New multi-coupling benzylic zinc reagents for the preparation of flexible aromatic compounds
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The benzylic zinc reagents 3a-c bearing a triflate group in o-, m- or p-position are new efficient multi-coupling reagents reacting stepwise with an aryl iodide (Ar1-I) and an arylzinc bromide (Ar2ZnBr) in the presence of the appropriate palladium catalyst and the suitable phosphine ligand leading to polyfunctional flexible aromatic products of type 5. This methodology is appropriate for applications in combinatorial chemistry.
- Rottlaender, Mario,Knochel, Paul
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p. 1749 - 1752
(2007/10/03)
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- A Facile Preparation of Aryl Triflates. Decomposition of Arenediazonium Tetrafluoroborate Salts in Trifluoromethanesulfonic Acid
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The thermal or photochemical decomposition of arenediazonium tetrafluoroborate salts n trifluoromethanesulfonic acid, with or without organic bases such as pyridine, provides aryl triflates in high yields.
- Yoneda, Norihiko,Fukuhara, Tsuyoshi,Mizokami, Takao,Suzuki, Akira
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p. 459 - 460
(2007/10/02)
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