- Greening the Valsartan Synthesis: Scale-up of Key Suzuki-Miyaura Coupling over Silia Cat DPP-Pd
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The study of the scale-up of the heterogeneous Suzuki-Miyaura coupling reaction in batch conditions between 2-chlorobenzonitrile and 4-tolylboronic acid, a key step in valsartan synthesis, to produce 4′-methyl-2- biphenylcarbonitrile over the SiliaCat DPP-Pd catalyst in ethanol under reflux allows to identify the optimal reaction conditions. The catalyst, regardless of limited Pd leaching, is not reusable, and the method can be effectively applied to the high yield synthesis of several coupling products, opening the route to efficient continuous coupling syntheses.
- Pandarus, Valerica,Desplantier-Giscard, Delphine,Gingras, Genevieve,Beland, Francois,Ciriminna, Rosaria,Pagliaro, Mario
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- Synthesis of dibenzopyranones through palladium-catalyzed directed C-H activation/carbonylation of 2-arylphenols
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Dibenzopyranones were synthesized by a palladium-catalyzed phenol-directed C-H activation/carbonylation of 2-phenylphenol derivatives in the presence of CO. Pd(OAc)2 was used as a catalyst and Cu(OAc)2 as a catalytic oxidant in the presence of air. Copyright
- Luo, Shuang,Luo, Fei-Xian,Zhang, Xi-Sha,Shi, Zhang-Jie
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- 10-Hydroxy-10,9-boroxarophenanthrenes: Versatile synthetic intermediates to 3,4-benzocoumarins and triaryls
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10-Hydroxy-10,9-boroxarophenanthrenes were obtained as unexpected major products upon BBr3-mediated O-demethylation of 2-methoxybiaryls. The formation likely proceeds via intramolecular electrophilic aromatic cyclization of a reactive dibromoaryloxyborane intermediate. Essentially quantitative yields of 10-hydroxy-10,9-boroxarophenanthrenes were also obtained from 2-hydroxybiaryl and BCl3/AlCl3 with use of a modified literature procedure. As synthetic intermediates, 10-hydroxy-10,9- boroxarophenanthrenes were efficiently converted to 3,4-benzocoumarins and triaryls through Pd-catalyzed CO insertion and Suzuki reaction.
- Zhou, Q. Jean,Worm, Karin,Dolle, Roland E.
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- Repetitive two-step method for oligoarene synthesis through rapid cross-coupling of hydroxyphenylboronic acids and anhydrides
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A two-step Suzuki-Miyaura coupling-Inflation procedure, which features the use of hydroxyphenylboronic acids or anhydrides in the palladium-catalyzed cross-coupling step, has been developed for the synthesis of oligoarenes. Copyright
- Ishikawa, Shunpei,Manabe, Kei
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- Suzuki coupling with ligandless palladium and potassium fluoride
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A ligandless palladium catalyzed Suzuki coupling reaction is described.
- Kabalka,Namboodiri,Wang
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- Synthetic method for multifunctionalized oligoarenes using pinacol esters of hydroxyphenylboronic acids
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A synthetic method for multifunctionalized oligoarenes using rapid Suzuki-Miyaura coupling of pinacol esters of hydroxyphenylboronic acids and subsequent triflation of the hydroxy group was developed. The Royal Society of Chemistry 2006.
- Ishikawa, Shunpei,Manabe, Kei
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- Palladium nanoparticles in ionic liquid by sputter deposition as catalysts for suzuki-miyaura coupling in water
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Palladium nanoparticles in an ionic liquid prepared readily by sputter deposition efficiently catalyze the Suzuki-Miyaura coupling of hydrophobic as well as hydrophilic aryl halides in water.
- Oda, Yoshiro,Hirano, Koji,Yoshii, Kazuki,Kuwabata, Susumu,Torimoto, Tsukasa,Miura, Masahiro
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- Ruthenium-catalyzed carbonylative C-H cyclization of 2-arylphenols: A novel synthetic route to 6 H-dibenzo[b,d]pyran-6-ones
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Catalytic carbonylative C-H cyclization of 2-arylphenols can be achieved in the presence of a ruthenium-based catalytic system. The process proceeds efficiently under balloon pressure of CO and produces variously substituted 6H-dibenzo[b,d]pyran-6-one compounds, typically in good to high yields. Functional groups such as the alkoxycarbonyl and acetyl groups as well as halogen atoms (F, Cl, and Br) are well tolerated during the reaction.
- Inamoto, Kiyofumi,Kadokawa, Jun,Kondo, Yoshinori
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- Pd-catalyzed protecting-group-free cross-couplings of iodophenols with atom-economic triarylbismuth reagents
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An efficient protocol for the protecting-group-free synthesis of unsymmetrical hydroxybiaryls via the Pd-catalyzed cross-couplings of unprotected iodophenols with triarylbismuth reagents is described. The presented protocols exhibits good to high yields of hydroxybiaryls.
- Rao, Maddali L.N.,Meka, Suresh
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- Exhaustive Reduction of Esters Enabled by Nickel Catalysis
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We report a one-step procedure to directly reduce unactivated aryl esters into their corresponding tolyl derivatives. This is achieved by an organosilane-mediated ester hydrosilylation reaction and subsequent Ni/NHC-catalyzed hydrogenolysis. The resulting conditions provide a direct and efficient alternative to multi-step procedures for this transformation that often require the use of hazardous metal hydrides. Applications in the synthesis of -CD3-containing products, derivatization of bioactive molecules, and chemoselective reduction in the presence of other C-O bonds are demonstrated.
- Cook, Adam,Prakash, Sekar,Zheng, Yan-Long,Newman, Stephen G.
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supporting information
p. 8109 - 8115
(2020/05/20)
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- Microwave-Promoted Pd-Catalyzed Synthesis of Dibenzofurans from Ortho-Arylphenols
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ortho-Aryl phenols, synthesized via protecting group free Suzuki–Miyaura coupling of ortho-halophenols and arene boronic acids, undergo a cyclization to dibenzofurans via oxidative C–H activation. The reaction proceeds under microwave irradiation in short reaction times using catalytic amounts of Pd(OAc)2 without additional ligands.
- Schmidt, Bernd,Riemer, Martin
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p. 1287 - 1297
(2017/03/27)
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- A highly efficient metal-free approach to: Meta - And multiple-substituted phenols via a simple oxidation of cyclohexenones
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A novel and efficient metal-free approach to substituted phenols has been disclosed from simple and readily available cyclohexenones and cyclohexenone equivalents. Dimethyl sulfoxide (DMSO), a simple and common organic reagent, was employed as a mild oxidant in this I2-catalysis, which significantly tolerates various substituents including some easily oxidizable or reducible functionalities. The challenging meta- and multiple-substituted phenols could be well prepared by this method. The metal-free and mild oxidation make this protocol very simple, practical, and easy to handle.
- Liang, Yu-Feng,Song, Song,Ai, Lingsheng,Li, Xinwei,Jiao, Ning
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supporting information
p. 6462 - 6467
(2018/06/08)
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- A New Route to Phenols: Palladium-Catalyzed Cyclization and Oxidation of γ,δ-Unsaturated Ketones
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We report a new strategy for the synthesis of phenols from acyclic unsaturated ketones in one pot. The reaction proceeds by palladium-catalyzed carbopalladation of an alkene with the enol form of the tethered ketone, generating a substituted cyclohexanone. Upon introduction of a terminal oxidant a palladium-catalyzed oxidation ensues to give the desired phenol. This approach allows the programming of phenol substituents on the acyclic substrate and therefore circumvents the limitations inherent in traditional syntheses of phenols.
- Samadi, Sadaf,Orellana, Arturo
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p. 2472 - 2475
(2016/08/25)
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- Homocoupling of iodoarenes and bromoalkanes using photoredox gold catalysis: A light enabled Au(III) reductive elimination
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The formation of homocoupled alkane byproducts have been identified in the reduction of bromoalkanes via photoredox gold catalysis with dimeric Au(I) complexes. This prompted further investigation into the mechanism of formation of these byproducts and the diversity of C-X bonds amenable to this transformation. Examples were found when considering bromoalkanes while a wide variety of iodoarenes underwent this process in good to excellent yields. The light enabled homocoupling of iodoarenes made possible by photoredox gold catalysis is reported.
- Tran, Huy,McCallum, Terry,Morin, Mathieu,Barriault, Louis
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supporting information
p. 4308 - 4311
(2016/09/09)
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- Synthesis of 2,2′-biphenols through direct C(sp2)-H hydroxylation of [1,1′-biphenyl]-2-ols
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A novel synthesis of diversely substituted 2,2′-biphenols through Pd(ii)-catalyzed, tBuOOH-oxidized, and hydroxyl-directed C(sp2)-H hydroxylation of [1,1′-biphenyl]-2-ols has been developed. Notably, this finding is distinct from previous reports in which [1,1′-biphenyl]-2-ols underwent an intramolecular C-H activation and C-O bond formation to afford dibenzofurans under the promotion of Pd(ii) but in the absence of tBuOOH.
- Duan, Shitao,Xu, Yuanshuang,Zhang, Xinying,Fan, Xuesen
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supporting information
p. 10529 - 10532
(2016/09/02)
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- Facile synthesis of 2-arylphenols via palladium-catalyzed cross-coupling of aryl iodides with 6-diazo-2-cyclohexenones
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2-Arylphenols were conveniently synthesized from aryl iodides and 6-diazo-2-cyclohexenones, in moderate to excellent yields, via tandem Pd-catalyzed cross-coupling/aromatization. The preliminary results for the corresponding enantioselective version showe
- Yang, Ke,Zhang, Jun,Li, Yun,Cheng, Bin,Zhao, Liang,Zhai, Hongbin
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supporting information
p. 808 - 811
(2013/03/28)
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- DERIVATIVES OF 6-SUBSTITUTED TRIAZOLOPYRIDAZINES AS REV-ERB AGONISTS
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The present invention provides novel 6-substituted [1,2,4]triazolo[4,3-b]pyridazines that are agonists of Rev-Erb. These compounds, and pharmaceutical compositions comprising the same, are suitable means for treating any disease wherein the activation of Rev-Erb has therapeutic effects, for instance in inflammatory and circadian rhythm-related disorders or cardiometabolic diseases.
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(2013/04/13)
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- Two-stage optimization of a supramolecular catalyst for catalytic asymmetric hydroboration
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Systematic changes, first to the structure of the catalyst scaffold and then to the ligating groups, are used to fine tune supramolecular catalysts to achieve high regioselectivity (95-98%) and high enantioselectivity (94-97% ee) across a series of meta-substituted styrenes varying in electronic character.
- Moteki, Shin A.,Toyama, Kazuya,Liu, Zeyu,Ma, Jing,Holmes, Andrea E.,Takacs, James M.
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supporting information; experimental part
p. 263 - 265
(2012/01/13)
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- The pyridyldiisopropylsilyl group: A masked functionality and directing group for monoselective ortho-Acyloxylation and ortho-Halogenation reactions of arenes
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A novel, easily removable and modifiable silicon-tethered pyridyldiisopropylsilyl directing group for C-H functionalizations of arenes has been developed. The installation of the pyridyldiisopropylsilyl group can efficiently be achieved via two complementary routes using easily available 2-(diisopropylsilyl)pyridine (5). The first strategy features a nucleophilic hydride substitution at the silicon atom in 5 with aryllithium reagents generated in situ from the corresponding aryl bromides or iodides. The second milder route exploits a highly efficient room-temperature rhodium(I)-catalyzed cross-coupling reaction between 5 and aryl iodides. The latter approach can be applied to the preparation of a wide range of pyridyldiisopropylsilyl- substituted arenes possessing a variety of functional groups, including those incompatible with organometallic reagents. The pyridyldiisopropylsilyl directing group allows for a highly efficient, regioselective palladium(II)-catalyzed mono-ortho-acyloxylation and ortho-halogenation of various aromatic compounds. Most importantly, the silicon-tethered directing group in both acyloxylated and halogenated products can easily be removed or efficiently converted into an array of other valuable functionalities. These transformations include protio-, deuterio-, halo-, boro-, and alkynyldesilylations, as well as a conversion of the directing group into the hydroxy functionality. In addition, the construction of aryl-aryl bonds via the Hiyama-Denmark cross-coupling reaction is feasible for the acetoxylated products. Moreover, the ortho-halogenated pyridyldiisopropylsilylarenes, bearing both nucleophilic pyridyldiisopropylsilyl and electrophilic aryl halide moieties, represent synthetically attractive 1,2-ambiphiles. A unique reactivity of these ambiphiles has been demonstrated in efficient syntheses of arylenediyne and benzosilole derivatives, as well as in a facile generation of benzyne. In addition, preliminary mechanistic studies of the acyloxylation and halogenation reactions have been performed. A trinuclear palladacycle intermediate has been isolated from a stoichiometric reaction between diisopropyl(phenyl)pyrid-2-ylsilane (3a) and palladium acetate. Furthermore, both C-H functionalization reactions exhibited equally high values of the intramolecular primary kinetic isotope effect (kH/k D=6.7). Based on these observations, a general mechanism involving the formation of a palladacycle via a C-H activation process as the rate-determining step has been proposed.
- Huang, Chunhui,Chernyak, Natalia,Dudnik, Alexander S.,Gevorgyan, Vladimir
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p. 1285 - 1305
(2011/07/07)
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- Well-defined air-stable palladium HASPO complexes for efficient Kumada-Corriu cross-couplings of (Hetero)aryl or alkenyl tosylates
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Palladium complexes of representative heteroatom-substituted secondary phosphine oxide (HASPO) preligands were synthesized and fully characterized, including X-ray crystal structure analysis. Importantly, these well-defined complexes served as highly efficient catalysts for Kumada-Corriu cross-coupling reactions of aryl, alkenyl, and even heteroaryl tosylates. Particularly, an air-stable catalyst derived from inexpensive PinP(O)H displayed a remarkably high catalytic efficacy, which resulted in cross-couplings at low catalyst loadings under exceedingly mild reaction conditions with ample scope.
- Ackermann, Lutz,Kapdi, Anant R.,Fenner, Sabine,Kornhaab, Christoph,Schulzke, Carola
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supporting information; experimental part
p. 2965 - 2971
(2011/05/05)
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- Oxidative cyclization of 2-arylphenols to dibenzofurans under Pd(II)/peroxybenzoate catalysis
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2-Arylphenols undergo intramolecular C-H bond activation/C-O bond formation to afford dibenzofuran derivatives under palladium catalysis in the presence of tert-butyl peroxybenzoate as an oxidant. Kinetic isotope effect experiments indicated that C-H bond cleavage is the rate-limiting step of the reaction.
- Wei, Ye,Yoshikai, Naohiko
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supporting information; scheme or table
p. 5504 - 5507
(2011/12/05)
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- SUBSTITUTED IMIDAZOLONE DERIVATIVES, PREPARATIONS AND USES
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The present invention relates to polysubstituted imidazolone derivatives, to the pharmaceutical compositions comprising them and to the therapeutic uses thereof in the human and animal health fields. The present invention also relates to a process for preparing these derivatives.
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(2010/02/16)
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- Negishi coupling strategy of a repetitive two-step method for oligoarene synthesis
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A novel repetitive two-step method for oligoarene synthesis, based on Negishi cross-coupling of zinciophenoxides or zinciopyridinoxides with aryl triflates and subsequent triflation of the hydroxy group, was developed. Reaction conditions were optimized for the preparation of the arylzinc compounds and the palladium-catalyzed cross-coupling step.
- Shimizu, Haruka,Manabe, Kei
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p. 5927 - 5931
(2007/10/03)
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- Chromium- and tungsten-triggered valence isomerism of cis-1-acyl-2-ethynylcyclopropanes via [3,3] sigmatropy of (2-acylcyclopropyl)vinylidene - Metal intermediates
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The reaction of cis vicinal acetylethynylcyclopropanes 1 with a catalytic amount of M(CO)5(THF) (M = Cr or W) in the presence of Et3N at room temperature gave ortho-substituted phenols 7 in good yields as valence isomerized products. In the absence of Et3N the reactions did not work at all. The reaction of a cyclopropane having an ester or an amide instead of an acetyl moiety with M(CO)5(THF) did not take place, whereas an ethynylvinylcyclopropane gave a mixture of 1- and 2-substituted 1,3,5-cycloheptatrienes. These valence isomerization reactions are assumed to proceed via the formation of vinylidene-metal intermediates 2 from terminal alkynyl moieties followed by [3,3]sigmatropy of 2 to give seven-membered carbene complexes 3. Copyright
- Ohe, Kouichi,Yokoi, Tomomi,Miki, Koji,Nishino, Fumiaki,Uemura, Sakae
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p. 526 - 527
(2007/10/03)
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- Palladium-catalyzed biaryl-coupling reaction of arylboronic acids in water using hydrophilic phosphine ligands
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Hydrophilic phosphine ligands possessing a carbohydrate side-chain, such as N-(4-diphenylphosphinophenyl)methyl gluconamide (9), N-[4-(2′-dicyclohexylphosphinobiphenyl)phenylmethyl] gluconamide (10), and N-[4-(2′-di-t-butylphosphinobiphenyl)]phenylmethyl gluconamide (11), were newly synthesized to carry out palladium-catalyzed biaryl coupling of arylboronic acids in a single aqueous medium. The catalyst prepared in situ from Pd(OAc)2 and 10 exhibited a higher efficiency than that of 9, 11, Ph2P(m-C6H4SO3Na) (TPPMS) or P(m-C6H4SO3Na)3 (TPPTS) for representative aryl bromides, chlorides, or triflates. The catalyst prepared in situ from Pd(OAc)2 (0.001mol%) and 10 (0.002mol%) achieved 96,000 TON in the reaction of p-tolylboronic acid with 4-bromoacetophenone in water.
- Nishimura, Masato,Ueda, Masato,Miyaura, Norio
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p. 5779 - 5787
(2007/10/03)
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- A palladium-catalyzed biaryl coupling of arylboronic acids in aqueous media using a gluconamide-substituted triphenylphosphine (GLCAphos) ligand
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A water-soluble phosphine ligand, N-(4-diphenyl-phosphino)phenylmethyl gluconamide (GLCAphos), was newly synthesized to perform the palladium- catalyzed biaryl coupling of arylboronic acids in a single aqueous media. The catalyst prepared from GLCAphos revealed higher activity than that synthesized from Ph2P(m-C6H4SO3Na) or P(m-C6H4SO3Na)3 for various haloarenes.
- Ueda, Masato,Nishimura, Masato,Miyaura, Norio
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p. 856 - 858
(2007/10/03)
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- Regioselective Arylation Reactions of Biphenyl-2-ols, Naphthols, and Benzylic Compounds with Aryl Halides under Palladium Catalysis
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Biphenyl-2-ols undergo regioselective mono- and diarylation upon a treatment with aryl iodides in the presence of a palladium catalyst in DMF using Cs2CO3 as a base to produce 1,1′ : 2′,1″-terphenyl-2-ol and 2′,6′-diphenylbiphenyl-2-ol and their derivatives. The reaction of 1-naphthol selectively occurs at its 8-position to give 8-aryl-1-naphthols. In the reaction of 2-naphthol with aryl bromides, diarylated compounds, 1-(2-arylphenyl)-2-naphthols, are formed as the single major products. Under similar conditions, benzyl ketones, phenylacetonitrile, and methyl phenylacetate are arylated at their benzylic position.
- Satoh, Tetsuya,Inoh, Jun-Ichi,Kawamura, Yoshiki,Kawamura, Yuichiro,Miura, Masahiro,Nomura, Masakatsu
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p. 2239 - 2246
(2007/10/03)
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- Benzo-fused lactams promote release of growth hormone
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There are disclosed certain novel compounds identified as benzo-fused lactams which promote the release of growth hormone in humans and animals. This property can be utilized to promote the growth of food animals to render the production of edible meat products more efficient, and in humans, to increase the stature of those afflicted with a lack of a normal secretion of natural growth hormone. Growth promoting compositions containing such benzo-fused lactams as the active ingredient therefore are also disclosed.
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- Benzo-fused lactams promote release of growth hormone
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There are disclosed certain novel compounds identified as benzo-fused lactams which promote the release of growth hormone in humans and animals. This property can be utilized to promote the growth of food animals to render the production of edible meat products more efficient, and in humans, to increase the stature of those afflicted with a lack of a normal secretion of natural growth hormone. The compounds are prepared by substitution of an amino-lactam with a substituted amide function. Growth promoting compositions containing such benzo-fused lactams as the active ingredient thereof are also disclosed. STR1 Where L is STR2
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- Benzo-fused lactams that promote the release of growth hormone
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There are disclosed certain novel compounds identified as benzo-fused lactams which promote the release of growth hormone in humans and animals. This property can be utilized to promote the growth of food animals to render the production of edible meat products more efficient, and in humans, to increase the stature of those afflicted with a lack of a normal secretion of natural growth hormone. Growth promoting compositions containing such benzo-fused lactams as the active ingredient thereof are also disclosed.
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