- Ru-catalyzed (E)-specific ortho-C-H alkenylation of arenecarboxylic acids by coupling with alkenyl bromides
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In the presence of [p-cymene)RuCl2]2, (E)-configured alkenyl bromides couple with aromatic carboxylates to form ortho-vinylbenzoic acids. This C-H vinylation proceeds in high yields without any activating phosphine ligands and has an excellent functional group tolerance. Starting from commonly available (E/Z)-mixtures of alkenyl bromides, (E)-configured vinyl arenes or dienes are formed exclusively. Mechanistic studies show that this selectivity is achieved because the (E)-configured alkenyl bromides undergo a smooth coupling, whereas the (Z)-isomers are rapidly eliminated with the formation of alkynes.
- Belitz, Florian,Goo?en, Lukas J.,Hu, Zhiyong,Papp, Florian,Zhang, Guodong
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supporting information
p. 3541 - 3545
(2021/05/31)
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- Synthesis and characterization of mesoporous organosilica supported palladium (SBA-Pr-NCQ-Pd) as an efficient nanocatalyst in the Mizoroki–Heck coupling reaction
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In the present study, the modification of a mesoporous organosilica nanocomposite SBA-15 (Santa Barbara Amorphous 15) was carried out in two steps, first through the surface functionalization of SBA-Pr-NH2 with 2-chloroquinoline-3-carbaldehyde to form SBA-Pr-NCQ, and then through a post-modification process with palladium ions. The target nanocompound structure of SBA-Pr-NCQ-Pd was characterized by different techniques (thermogravimetric analysis, X-ray diffraction, scanning electron microscopy, Energy-dispersive X-ray spectroscopy (EDX), and Fourier transform infrared spectroscopy). The catalytic performance of the porous inorganic–organic hybrid nanocomposite (SBA-Pr-NCQ-Pd) in one of the most important carbon–carbon bond-forming processes, the Mizoroki–Heck coupling reaction of aryl halides and methacrylate in water/ethanol media, was examined. Compared to previous reports, this protocol afforded some advantages, such as high yields of products, short reaction times, catalyst stability without leaching, simple methodology, easy workup, and greener conditions. Also, the nanocatalyst can be easily separated from the reaction mixture and reused several times without a significant decrease in activity and promises economic as well as environmental benefits.
- Moradi, Razieh,Mohammadi Ziarani, Ghodsi,Badiei, Alireza,Mohajer, Fatemeh
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- Design and chemical synthesis of root gravitropism inhibitors: Bridged analogues of ku-76 have more potent activity
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Previously, we found (2Z,4E)-5-phenylpenta-2,4-dienoic acid (ku-76) to be a selective inhibitor of root gravitropic bending of lettuce radicles at 5 μM, with no concomitant growth inhibition, and revealed the structure–activity relationship in this inhibitory activity. The conformation of ku-76 is flexible owing to the open-chain structure of pentan-2,4-dienoic acid with freely rotating single bonds, and the (2Z)-alkene moiety may be isomerized by external factors. To develop more potent inhibitors and obtain insight into the target biomolecules, various analogues of ku-76, fixed through conformation and/or configuration, were synthesized and evaluated. Stereochemical fixation was effective in improving the potency of gravitropic bending inhibition. Finally, we found highly potent conformational and/or configurational analogues (ku-257, ku-294 and ku-308), that did not inhibit root growth. The inhibition of root curvature by these analogues was comparable to that of naptalam.
- Fujii, Yoshiharu,Iwata, Takayuki,Kano, Arihiro,Kodama, Kozue,Makigawa, Saki,Matsumoto, Kenji,Morita, Miyo Terao,Shindo, Mitsuru,Sugiyama, Hiromi,Wasano, Naoya
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- COMPOUNDS FOR MODULATING DDAH AND ADMA LEVELS, AS WELL AS METHODS OF USING THEREOF TO TREAT DISEASE
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Disclosed are compounds that can modulate DDAH and the amount of asymmetric dimethylarginine (ADMA) in a subject. Also provided are pharmaceutical compositions comprising these compounds, as well as methods of using these compositions to treat and/or prevent diseases associated with elevated or low levels of DDAH and ADMA.
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- trans-Cyclooctenes as Halolactonization Catalysts
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The strained olefins in trans-cyclooctenes serve as efficient catalysts for halolactonizations, including bromolactonizations and iodolactonizations. The trans-cyclooctene framework is essential for excellent catalytic performance, and the substituents also play important roles in determining efficiency. These results are the first demonstration of catalysis by a trans-cyclooctene.
- Einaru, Shunsuke,Shitamichi, Kenta,Nagano, Tagui,Matsumoto, Akira,Asano, Keisuke,Matsubara, Seijiro
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supporting information
p. 13863 - 13867
(2018/09/27)
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- An Easy-to-Machine Electrochemical Flow Microreactor: Efficient Synthesis of Isoindolinone and Flow Functionalization
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Flow electrochemistry is an efficient methodology to generate radical intermediates. An electrochemical flow microreactor has been designed and manufactured to improve the efficiency of electrochemical flow reactions. With this device only little or no supporting electrolytes are needed, making processes less costly and enabling easier purification. This is demonstrated by the facile synthesis of amidyl radicals used in intramolecular hydroaminations to produce isoindolinones. The combination with inline mass spectrometry facilitates a much easier combination of chemical steps in a single flow process.
- Folgueiras-Amador, Ana A.,Philipps, Kai,Guilbaud, Sébastien,Poelakker, Jarno,Wirth, Thomas
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supporting information
p. 15446 - 15450
(2017/11/10)
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- Intramolecular Hydroamidation of ortho-Vinyl Benzamides Promoted by Potassium tert-Butoxide/N,N-Dimethylformamide
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An intramolecular hydroamidation of ortho-vinyl benzamides had been developed. The reaction was promoted efficiently by potassium tert-butoxide and N,N-dimethylformamide without the need for strong oxidants or transition-metal catalysts. A series of dihyd
- Chen, Zhen-Yu,Wu, Liang-Yu,Fang, Hai-Sheng,Zhang, Ting,Mao, Zhi-Feng,Zou, Yong,Zhang, Xue-Jing,Yan, Ming
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p. 3894 - 3899
(2017/10/07)
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- Synthesis of Secondary Unsaturated Lactams via an Aza-Heck Reaction
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The preparation of unsaturated secondary lactams via the palladium-catalyzed cyclization of O-phenyl hydroxamates onto a pendent alkene is reported. This method provides rapid access to a broad range of lactams that are widely useful building blocks in alkaloid synthesis. Mechanistic studies support an aza-Heck-type pathway.
- Shuler, Scott A.,Yin, Guoyin,Krause, Sarah B.,Vesper, Caroline M.,Watson, Donald A.
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supporting information
p. 13830 - 13833
(2016/11/06)
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- Copper-Catalyzed Amino Lactonization and Amino Oxygenation of Alkenes Using O-Benzoylhydroxylamines
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A copper-catalyzed amino lactonization of unsaturated carboxylic acids has been achieved as well as the analogous intermolecular three-component amino oxygenation of olefins. The transformation features mild conditions and a remarkably broad substrate sco
- Hemric, Brett N.,Shen, Kun,Wang, Qiu
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supporting information
p. 5813 - 5816
(2016/06/09)
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- Manganese-Catalyzed ortho-C?H Alkenylation of Aromatic N?H Imidates with Alkynes: Versatile Access to Mono-Alkenylated Aromatic Nitriles
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So far, the direct C?H alkenylation of aromatic nitriles with alkynes has not been achieved. Herein, we discribe the first manganese-catalyzed C?H alkenylation of aromatic N?H imidates to access mono-alkenylated aromatic nitriles. The reaction is accelerated by the presence of a catalytic amount of sodium pivalate. This protocol is also highlighted by the simple catalytic system, good compatibility of functional groups, and excellent mono-/dialkenylation selectivity as well as E/Z stereoselectivity. (Figure presented.).
- Yang, Xiaoxu,Jin, Xiqing,Wang, Congyang
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p. 2436 - 2442
(2016/08/16)
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- Cobalt(II)-Catalyzed Csp2-H Alkynylation/Annulation with Terminal Alkynes: Selective Access to 3-Methyleneisoindolin-1-one
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A highly efficient cobalt(II)-catalyzed alkynylation/annulation of terminal alkynes assisted by an N,O-bidentate directing group is described. This protocol is characterized by wide substrate scope utilizing cheap cobalt catalysts, and offers a new approa
- Zhang, Lin-Bao,Hao, Xin-Qi,Liu, Zhan-Jiang,Zheng, Xin-Xiang,Zhang, Shou-Kun,Niu, Jun-Long,Song, Mao-Ping
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supporting information
p. 10012 - 10015
(2015/08/19)
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- NHC-catalyzed oxidative cyclization reaction for the synthesis of 3-substituted phthalides
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An efficient NHC-catalyzed domino oxidation/oxa-Michael addition reaction of 2-alkenylbenzaldehydes has been developed to afford 3-substituted phthalides bearing a C3-stereogenic center with a broad substrate scope and wide functional group tolerance. The preliminary results of the asymmetric process have been provided as well. the Partner Organisations 2014.
- Youn, So Won,Song, Hyoung Sub,Park, Jong Hyub
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p. 2388 - 2393
(2014/04/03)
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- Multicomponent, flow diazotization/mizoroki-heck coupling protocol: Dispelling myths about working with diazonium salts
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A single pass flow diazotization/Mizoroki-Heck protocol has been developed for the production of cinnimoyl and styryl products. The factors that govern aryl diazonium salt stability have been examined in detail leading to the development of a MeOH/DMF co-solvent system in which the diazonium salts can be generated in the presence of all other reaction components and then coupled selectively to give the desired products. Finally the key role of the reaction quench for flow reactions has been demonstrated.
- Nalivela, Kumara S.,Tilley, Michael,McGuire, Michael A.,Organ, Michael G.
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supporting information
p. 6603 - 6607
(2014/06/09)
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- A facile and efficient method for the synthesis of N-substituted 3-oxoisoindoline-1-carbonitrile derivatives catalyzed by sulfamic acid
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A new and efficient method for the synthesis of N-substituted 3-oxoisoindoline-1-carbonitrile derivatives by a one-pot, three-component condensation reaction of 2-carboxybenzaldehyde, primary amine, and TMSCN in the presence of 10 mol % sulfamic acid (NH2SO3H) as the catalyst in EtOH under reflux temperature is described. The process is simple and environmentally benign and the catalyst is commercially available and inexpensive. ARKAT-USA, Inc.
- Hu, Ling-Jun,Zhan, Zha-Jun,Lei, Min,Hu, Li-Hong
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p. 189 - 198
(2013/06/27)
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- Heck-type reaction of aryldiazonium silica sulfates
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Aryldiazonium silica sulfates were employed as new and efficient reagents for Heck-type arylation reactions with styrene and methyl acrylate. The reactions were carried out in an organic solvent, in the presence of Pd(OAc)2 as precatalyst without use of base and free ligand. The trans isomers of desired products, methyl cinnamates and stilbenes, were obtained with full conversion. Use of a catalytic amount of Pd(OAc)2 produced the corresponding products in short reaction times and excellent yields. Springer-Verlag 2011.
- Pirisedigh, Azadeh,Zarei, Amin,Seyedjamali, Hojjat,Khazdooz, Leila,Hajipour, Abdol R.
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experimental part
p. 791 - 795
(2012/09/05)
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- Expeditious synthesis of 3,4-dihydroisocoumarins and phthalides using the Heck-Matsuda reaction
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Several 3,4-dihydroisocoumarins and phthalides were synthesized by an effective Heck-Matsuda reaction involving an ortho carboxybenzenediazonium salt with a series of styrenes bearing electron donating and electron withdrawing groups, methylvinyl ketone,
- Da Penha, Eduardo T.,Forni, José Augusto,Biajoli, André F.P.,Correia, Carlos Roque D.
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scheme or table
p. 6342 - 6345
(2011/12/21)
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- Rhodium-catalyzed regioselective olefination directed by a carboxylic group
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The ortho-olefination of benzoic acids can be achieved effectively through rhodium-catalyzed oxidative coupling with alkenes. The carboxylic group is readily removable to allow ortho-olefination/decarboxylation in one pot. α,β-Unsaturated carboxylic acids
- Mochida, Satoshi,Hirano, Koji,Satoh, Tetsuya,Miura, Masahiro
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experimental part
p. 3024 - 3033
(2011/06/24)
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- Rh(III)-catalyzed Directed C-H Olefination using an oxidizing directing group: Mild, efficient, and versatile
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An efficient Rh(III)-catalyzed oxidative olefination by directed C-H bond activation of N-methoxybenzamides is reported. In this mild, practical, selective, and high-yielding process, the N-O bond acts as an internal oxidant. In addition, simply changing the substituent of the directing/oxidizing group results in the selective formation of valuable tetrahydroisoquinolinone products.
- Rakshit, Souvik,Grohmann, Christoph,Besset, Tatiana,Glorius, Frank
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p. 2350 - 2353
(2011/05/04)
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- Selenium-mediated synthesis of biaryls through rearrangement
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"Chemical Equation Presented" A new cyclization of β-keto ester substituted stilbene derivatives using selenium electrophiles in the presence of Lewis acids is described. Substituted naphthols are obtained through cyclization and subsequent 1,2-rearrangement of aryl groups under very mild reaction conditions.
- Shahzad, Sohail A.,Vivant, Clotilde,Wirth, Thomas
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supporting information; experimental part
p. 1364 - 1367
(2010/06/17)
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- Diselenide- and disulfide-mediated synthesis of isocoumarins
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Cyclizations of stilbenecarboxylic acids to the corresponding isocoumarin derivatives using diselenide or disulfide reagents have been developed. By employing bis(triflouroacetoxy)iodobenzene as oxidant for the 6-endo-trig cyclizations a variety of dihydroisocoumarins have been prepared in good yields. This method is capable of forming isocoumarins and dihydroisocoumarin derivatives by a cyclization-elimination route.
- Shahzad, Sohail A.,Venin, Claire,Wirth, Thomas
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experimental part
p. 3465 - 3472
(2010/09/07)
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- Efficient Regio- And Stereoselective Synthesis of 5-Alkyl(aryl)idene- and 5-[Iodoalkyl(aryl)idene]-1H-pyrrol-2(5//)-ones via Electrophilic Cyclization
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A variety of substituted 5-alkyl(aryl)idene-and 5-[1o-doalkyl(aryl)idene]- 1ff-pyrrol-2(5H)-ones were readily prepared with good yields under very mild reaction conditions by the iodocy- clization of (2Z,4E)-dienamides and (Z)-alk-2-en-4-ynamides with iod
- Cherry, Khalil,Duchene, Alain,Thibonnet, Jerome,Anselmi, Jean-Luc Parrain Elsa,Abarbri, Mohamed
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experimental part
p. 257 - 270
(2009/06/19)
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- Unusually stable, versatile, and pure arenediazonium tosylates: Their preparation, structures, and synthetic applicability
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(Graph Presented) A new, simple, and effective method for the diazotization of a wide range of arylamines has been developed by using a polymer-supported diazotization agent in the presence of p-toluenesulfonic acid. Various pure arenediazonium tosylates with unusual stabilities can be easily prepared by this method. As a result, these salts are useful and versatile substrates for subsequent transformations, such as halogenation and Heck-type reactions. The unusual stabilities of arenediazonium tosylates are also preliminarily discussed with their X-ray structures.
- Filimonov, Victor D.,Trusova, Marina,Postnikov, Pavel,Krasnokutskaya, Elena A.,Lee, Young Min,Hwang, Ho Yun,Kim, Hyunuk,Chi, Ki-Whan
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supporting information; experimental part
p. 3961 - 3964
(2009/05/30)
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- Discovery of phenyl alanine derived ketoamides carrying benzoyl residues as novel calpain inhibitors
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Novel calpain inhibitors derived from phenyl alanine aldehydes or ketoamides carrying a benzoyl residue were prepared and evaluated for their biological potency. A brief structure-activity relationship elucidated the importance of ortho-substitutents in t
- Lubisch, Wilfried,Moeller
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p. 1335 - 1338
(2007/10/03)
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- Benzamidoaldehydes and their use as cysteine protease inhibitors
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Compounds of the formula where R1, R2, R3, X and n are as defined in the description, are inhibitors of cysteine protease.
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- Unexpected rearrangements in the synthesis of arylidene- or alkylidene-2-thiophthalides
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Mechanistic studies concerning the reaction by which poly(isothianaphthene) (PITN) is synthesized in one step from commercially available monomers by reacting them with phosphorus pentasulphide (P4S10), have led to the idea of synthesizing a chain-stopper molecule which should give rise to suitable quinoid model compounds for PITN. Within this context benzylidenedithiophthalide and pentylidenedithiophthalide were chosen as target molecules. The unexpected rearrangements and the control of these rearrangements in the synthesis of benzylidenedithiophthalide and pentylidenedithiophthalide are reported.
- Paulussen, Harald,Adriaensens, Peter,Vanderzande, Dirk,Gelan, Jan
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p. 11867 - 11878
(2007/10/03)
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- Base-catalyzed ring openings of benzocyclobutenones and -ols
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The base-catalyzed ring opening of a number of isomeric E- and Z-benzylidenebenzocyclobutenones and -ols has been studied in both protic and aprotic solvents.Cleavage of the C1-C2 bond results in the formation of stilbenes with mainly, and at times exclusively, retained stereochemistry.For the alcohols, these results point to an oxyanion-induced carbon-carbon bond cleavage leading to a vinyl anion that is protonated with retention of configuration in the protic solvents rather than to an electrocyclic ring opening to an alkoxy o-quinodimethane.Reaction of the Z isomer of benzylidenebenzocyclobutenol with methyllithium in THF at 20 deg C causes isomerization to the E isomer, cleavage of the C1-C2 bond, and recyclization of the resultant isomerized vinyl anion. - Key words: benzylidenebenzocyclobutenones, base-catalyzed ring opening; benzylidenebenzocyclobutenols, base-catalyzed ring opening.
- Bradley, J. C.,Durst, T.
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p. 1660 - 1665
(2007/10/02)
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- Analysis of the 13C and 1H Spectra of Mixtures of Benzylidene Derivatives
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The 1H and 13C NMR spectra of methyl (E)-2,3-diphenylprop-2-enoate and methyl (E)-2-(2-phenylethenyl)benzoate resulting from the electrocyclic ring opening of benzocyclobutenone starting materials have been assigned.A combination of direct detection 2D NMR techniques, COSY, HETCOR, and FLOCK, provided the assignments of the 1H and 13C resonances. - Keywords: NMR 1H NMR 13C NMR Benzylidene derivatives
- Bradley, J. C.,Williams, A. J.
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p. 496 - 498
(2007/10/02)
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- Stereospecific Formation of 2-benzoic Acids in an Unusual Reaction of Thiophthalides with Aldehydes
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The reaction of thiophthalides 1 with aldehydes 3 in the presence of lithium tert-butoxide at -60 deg C to 25 deg C results in the stereospecific formation of only trans 2-(alk-1'-enyl)benzoic acids 4 in fairly good yields in one-pot operations.This react
- Mal, Dipakranjan,Majumdar, Gita,Pal, Ranjan
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p. 1115 - 1116
(2007/10/02)
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- Synthesis of Isocoumarin, 1-Isoquinolone and 4(1H)-Quinolone Derivatives via Seleno-intermediates
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The reaction of 2-styrylbenzoic acid 2 with N-phenylselenosuccinimide (N-PPS) affords 3-phenyl-iso-coumarin derivatives 3 and 3,4-dihydro-3-phenyl-4-(phenylseleno)isocoumarins 4 via selenolactonization.The reaction of 2-styrylbenzamides 5 and 1-(2-aminoph
- Izumi, Taeko,Morishita, Nobuya
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p. 145 - 152
(2007/10/02)
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- Process for the arylation of olefins
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Substituted olefins of the formula (I) STR1 are prepared by reaction of a compound of the formula (II) STR2 with a compound of the formula (III) in the presence of an organic and/or inorganic palladium salt as a catalyst using water and/or an alcohol as a solvent, the substituents and indices being defined in the disclosure.
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- Synthetic Application of Lithiation Reaction: Part XVIII - Synthesis of (+/-)-3,4-Dihydro-3-phenylisocoumarin and Aglycone of (+/-)-Dihydrohomalicine
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N-Methylbenzamide on lithiation with n-butyllithium followed by reaction with N-methylformanilide gives compound (1), which on hydrolysis with dil.HCl furnishes 2-formylbenzoic acid (2).This acid on reaction with benzylidenetriphenylphosphorane gives stil
- Narasimhan, N. S.,Mali, R. S.,Kulkarni, B. K.
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p. 850 - 852
(2007/10/02)
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- Formation od some 3-Aryl-3,4-dihydroisocoumarins by Thermal Ring Closure of Stilbene-2-carboxylic Acids
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When heated at 200 deg C, cis- and trans-4'- and 2'-methoxystilbene-2-carboxylic acids have been converted into the title compounds in varying yields, as has trans-4'-hydroxystilbene-2-carboxylic acid.On the other hand, trans-4'-nitrostilbene-2-carboxylic acid affords 3-(4-nitrobenzyl)phthalide.Mass spectrometry provides a simple method of distinguishing between the dihydroisocoumarins and phthalides.
- Bellinger, Geoffrey C. A.,Campbell, William E.,Giles, Robin G. F.,Tobias, Julius D.
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p. 2819 - 2826
(2007/10/02)
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- Palladium(0)-Catalyzed Arylation of Olefins by Arylamines and an Alkyl Nitrite
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Various olefins were arylated by the combination of arylamines and tert-butyl nitrite under palladium catalysis in the presence of acid such as monochloroacetic or acetic.The reaction proceeded in good yields without serious effects from substituents on either the olefinic substrates or the arylamines, including 3-aminopyridine.
- Kikukawa, Kiyoshi,Maemura, Koji,Kiseki, Yasuyuki,Wada, Fumio,Matsuda, Tsutomu,Giam, Choo S.
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p. 4885 - 4888
(2007/10/02)
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