- Hydrosilane-Mediated Electrochemical Reduction of Amides
-
Electrochemical reduction of amides was achieved by using a hydrosilane without any toxic or expensive metals. The key reactive ketyl radical intermediate was generated by cathodic reduction. Continuous reaction with anodically generated silyl radicals or zinc bromide resulted in chemoselective deoxygenation to give the corresponding amines.
- Okamoto, Kazuhiro,Nagahara, Shingo,Imada, Yasushi,Narita, Risako,Kitano, Yoshikazu,Chiba, Kazuhiro
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p. 15992 - 16000
(2021/07/20)
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- Bisulfite Addition Compounds as Substrates for Reductive Aminations in Water
-
Highly valued products resulting from reductive aminations utilizing shelf-stable bisulfite addition compounds of aldehydes can be made under aqueous micellar catalysis conditions. Readily available α-picolineborane serves as the stoichiometric hydride source. Recycling of the aqueous reaction medium is easily accomplished, and several applications to targets in the pharmaceutical industry are documented.
- Bailey, J. Daniel,Iyer, Karthik S.,Leahy, David K.,Li, Xiaohan,Lipshutz, Bruce H.,Thakore, Ruchita R.
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supporting information
p. 7205 - 7208
(2021/09/22)
-
- Covalent Organic Frameworks toward Diverse Photocatalytic Aerobic Oxidations
-
Photoactive two-dimensional covalent organic frameworks (2D-COFs) have become promising heterogenous photocatalysts in visible-light-driven organic transformations. Herein, a visible-light-driven selective aerobic oxidation of various small organic molecules by using 2D-COFs as the photocatalyst was developed. In this protocol, due to the remarkable photocatalytic capability of hydrazone-based 2D-COF-1 on molecular oxygen activation, a wide range of amides, quinolones, heterocyclic compounds, and sulfoxides were obtained with high efficiency and excellent functional group tolerance under very mild reaction conditions. Furthermore, benefiting from the inherent advantage of heterogenous photocatalysis, prominent sustainability and easy photocatalyst recyclability, a drug molecule (modafinil) and an oxidized mustard gas simulant (2-chloroethyl ethyl sulfoxide) were selectively and easily obtained in scale-up reactions. Mechanistic investigations were conducted using radical quenching experiments and in situ ESR spectroscopy, all corroborating the proposed role of 2D-COF-1 in photocatalytic cycle.
- Liu, Shuyang,Tian, Miao,Bu, Xiubin,Tian, Hua,Yang, Xiaobo
-
supporting information
p. 7738 - 7744
(2021/05/07)
-
- B(C6F5)3-Catalyzed Highly Chemoselective Reduction of Isatins: Synthesis of Indolin-3-ones and Indolines
-
A chemo- and site-selective reduction reaction of isatin derivatives using catalyst B(C6F5)3 and hydrosilanes is described. This transformation is operationally simple, proceeds under mild conditions, and is resistant to various functional groups. Thus, this efficient reaction using a combination of B(C6F5)3 and BnMe2SiH or B(C6F5)3 and Et2SiH2 could potentially be utilized to produce various indolin-3-ones and indolines, without the need for multistep procedures and metal catalysis conditions.
- Jeong, Hyojin,Han, Nara,Hwang, Dong Wook,Ko, Haye Min
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p. 8150 - 8155
(2020/11/02)
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- Manganese-Catalyzed Regioselective Dehydrogenative C-versus N-Alkylation Enabled by a Solvent Switch: Experiment and Computation
-
The first base metal-catalyzed regioselective dehydrogenative alkylation of indolines using readily available alcohols as the alkylating reagent is reported. A single air-and moisture-stable manganese catalyst provides access to either C3-or N-alkylated indoles depending on the solvent used. Mechanistic studies indicate that the reaction takes place through a combined acceptorless dehydrogenation and hydrogen autotransfer strategy.
- Borghs, Jannik C.,Zubar, Viktoriia,Zubar, Viktoriia,Azofra, Luis Miguel,Sklyaruk, Jan,Rueping, Magnus,Rueping, Magnus
-
supporting information
p. 4222 - 4227
(2020/06/04)
-
- One-pot heteroarene synthesis based on ruthenium-on-carbon-catalyzed oxidative aromatization using oxygen
-
Various heteroarenes, such as indole, carbazole, dibenzofuran, dibenzothiophene, etc., were easily constructed by the Diels-Alder reaction of the corresponding vinyl-substituted pyrrole, indole, benzofuran or benzothiophene with the dienophiles and the su
- Sajiki, Hironao,Sawama, Yoshinari,Yamada, Yutaro,Yamamoto, Yuta
-
supporting information
p. 1419 - 1423
(2020/12/28)
-
- A NEW METHOD FOR SYNTHESIS OF C- 5 ALKYLATED INDOLINE AND INDOLE DERIVATIVES
-
Invention relates to a practical and easy synthesis method for the alkylation of C-5 position of indoline and indole ring for use in chemistry sector, medicine industry, pharmacy sector, and new intermediate products and products having use potential in i
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-
Page/Page column 9
(2020/03/23)
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- B(C6F5)3-Catalyzed Deoxygenative Reduction of Amides to Amines with Ammonia Borane
-
The first B(C6F5)3-catalyzed deoxygenative reduction of amides into the corresponding amines with readily accessible and stable ammonia borane (AB) as a reducing agent under mild reaction conditions is reported. This metal-free protocol provides facile access to a wide range of structurally diverse amine products in good to excellent yields, and various functional groups including those that are reduction-sensitive were well tolerated. This new method is also applicable to chiral amide substrates without erosion of the enantiomeric purity. The role of BF3 ? OEt2 co-catalyst in this reaction is to activate the amide carbonyl group via the in situ formation of an amide-boron adduct. (Figure presented.).
- Pan, Yixiao,Luo, Zhenli,Han, Jiahong,Xu, Xin,Chen, Changjun,Zhao, Haoqiang,Xu, Lijin,Fan, Qinghua,Xiao, Jianliang
-
supporting information
p. 2301 - 2308
(2019/01/30)
-
- Ru-Catalyzed Deoxygenative Transfer Hydrogenation of Amides to Amines with Formic Acid/Triethylamine
-
A ruthenium(II)-catalyzed deoxygenative transfer hydrogenation of amides to amines using HCO2H/NEt3 as the reducing agent is reported for the first time. The catalyst system consisting of [Ru(2-methylallyl)2(COD)], 1,1,1-tris(diphenylphosphinomethyl) ethane (triphos) and Bis(trifluoromethane sulfonimide) (HNTf2) performed well for deoxygenative reduction of various secondary and tertiary amides into the corresponding amines in high yields with excellent selectivities, and exhibits high tolerance toward functional groups including those that are reduction-sensitive. The choice of hydrogen source and acid co-catalyst is critical for catalysis. Mechanistic studies suggest that the reductive amination of the in situ generated alcohol and amine via borrowing hydrogen is the dominant pathway. (Figure presented.).
- Pan, Yixiao,Luo, Zhenli,Xu, Xin,Zhao, Haoqiang,Han, Jiahong,Xu, Lijin,Fan, Qinghua,Xiao, Jianliang
-
supporting information
p. 3800 - 3806
(2019/07/12)
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- Frustrated Lewis Pair Catalyzed Hydrogenation of Amides: Halides as Active Lewis Base in the Metal-Free Hydrogen Activation
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A method for the metal-free reduction of carboxylic amides using oxalyl chloride as an activating agent and hydrogen as the final reductant is introduced. The reaction proceeds via the hydrogen splitting by B(2,6-F2-C6H3)3 in combination with chloride as the Lewis base. Density functional theory calculations support the unprecedented role of halides as active Lewis base components in the frustrated Lewis pair mediated hydrogen activation. The reaction displays broad substrate scope for tertiary benzoic acid amides and α-branched carboxamides.
- Sitte, Nikolai A.,Bursch, Markus,Grimme, Stefan,Paradies, Jan
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p. 159 - 162
(2019/01/04)
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- Selective C-H Olefination of Indolines (C5) and Tetrahydroquinolines (C6) by Pd/S,O-Ligand Catalysis
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Herein, we report a highly selective C-H olefination of directing-group-free indolines (C5) and tetrahydroquinolines (C6) by Pd/S,O-ligand catalysis. In the presence of the S,O-ligand, a wide range of challenging indolines, tetrahydroquinolines, and olefins was efficiently olefinated under mild reaction conditions. The synthetic potential of this methodology was demonstrated by the efficient olefination of several indoline-based natural products.
- Jia, Wen-Liang,Westerveld, Nick,Wong, Kit Ming,Morsch, Thomas,Hakkennes, Matthijs,Naksomboon, Kananat,Fernández-Ibá?ez, M. ángeles
-
supporting information
p. 9339 - 9342
(2019/11/21)
-
- Access to C5-Alkylated Indolines/Indoles via Michael-Type Friedel-Crafts Alkylation Using Aryl-Nitroolefins
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A straightforward synthetic route toward C5-alkylated indolines/indoles has been developed. The strategy is composed of Zn(OTf)2-catalyzed Friedel-Crafts alkylation of N-benzylindolines with nitroolefins, and a series of diverse indolines was first obtained in up to 99% yield. This reaction provides a direct and practical route to a variety of the C5-alkylated indolines which were also utilized for accessing corresponding indoles. Indoline derivatives with free NH groups could be obtained through an N-deprotection reaction. Moreover, the primary alkyl nitro groups in both indolines and indoles are amenable to further synthetic elaborations, thereby broadening the diversity of the products.
- Ertugrul, Berrak,Kilic, Haydar,Lafzi, Farrokh,Saracoglu, Nurullah
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p. 9018 - 9038
(2018/06/27)
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- Dehydrogenative Aromatization and Sulfonylation of Pyrrolidines: Orthogonal Reactivity in Photoredox Catalysis
-
Oxidative dehydrogenative aromatization and selective sulfonylation reactions of N-heterocycles under visible-light photoredox catalysis were established. The mild reaction conditions make this approach an appealing and versatile strategy to functionalize/oxidize pyrrolidines whereby arylsulfonyl chlorides were identified to be both catalyst regeneration and sulfonylation reagents.
- Muralirajan, Krishnamoorthy,Kancherla, Rajesh,Rueping, Magnus
-
supporting information
p. 14787 - 14791
(2018/10/20)
-
- A by a process for preparing amine derivatives of green method (by machine translation)
-
The invention discloses a by a process for preparing amine derivatives of green method, dumping with amine compound in a non-transition metal catalyst under solvent-free conditions and through the controllable high selection dehydration alkylation reaction different amine derivatives, a non-transition metal catalyst is a halogenated hydrocarbon, halogenated hydrocarbon in an amount of 1 - 50 μM %, under the catalysis of the mellow and amine in halogenated hydrocarbon can be directly performed by the amine derivative dehydration reaction, the reaction temperature is 100 - 180 °C, the reaction time is 12 - 48 hours, the by-product is water, the reaction needs to be carried out under the protection of inert gas, simple conditions, easy to operate, the by-product is water, the reaction selectivity is controllable, the target high selectivity. Requirements for reaction condition of relatively low, primary and secondary alcohol can be used for the alkylation reagent, is suitable for the dehydration of the primary and secondary amines single alkylation reaction, is also suitable for the dehydration of the double alkylation reaction of a primary amine, with wider scope, should also has certain research and industrial application prospect. (by machine translation)
- -
-
Paragraph 0132 - 0135
(2017/08/14)
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- Nucleophilic Amination of Methoxy Arenes Promoted by a Sodium Hydride/Iodide Composite
-
A method for the nucleophilic amination of methoxy arenes was established by using sodium hydride (NaH) in the presence of lithium iodide (LiI). This method offers an efficient route to benzannulated nitrogen heterocycles. Mechanistic studies showed that the reaction proceeds through an unusual concerted nucleophilic aromatic substitution.
- Kaga, Atsushi,Hayashi, Hirohito,Hakamata, Hiroyuki,Oi, Miku,Uchiyama, Masanobu,Takita, Ryo,Chiba, Shunsuke
-
supporting information
p. 11807 - 11811
(2017/09/20)
-
- A silodosin intermediate and its preparation method, and the intermediate for method of preparation of the silodosin
-
The invention relates to the field of compound synthesis and especially relates to a silodosin intermediate, a preparation method of the silodosin intermediate, and a method for preparing silodosin from the silodosin intermediate. The method for preparing silodosin from the silodosin intermediate has the characteristics of economy, safety, high purity and high yield and is suitable for large-scale industrial production.
- -
-
Paragraph 0120-0129
(2017/08/26)
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- Divergent dehydrogenative coupling of indolines with alcohols
-
The dehydrogenative coupling of indolines with alcohols catalyzed by an iridium complex has been achieved to afford both N- and C3-alkylated indoles selectively, by simply changing the addition time of a base additive. The iridacycle catalyst plays multiple roles in these reactions, which dehydrogenates both amines and alcohols and catalyzes the coupling reactions. Mechanistic studies reveal that a borrowing hydrogen-dehydrogenation process and a dehydrogenationborrowing hydrogen process are involved in N-alkylation and C3-alkylation reactions, respectively. The C3-alkylation reaction involves the direct coupling of two sp3 carbon centers.
- Jiang, Xue,Tang, Weijun,Xue, Dong,Xiao, Jianliang,Wang, Chao
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p. 1831 - 1835
(2017/08/01)
-
- Unsupported Nanoporous Gold Catalyst for Chemoselective Hydrogenation Reactions under Low Pressure: Effect of Residual Silver on the Reaction
-
For the first time, H-H dissociation on an unsupported nanoporous gold (AuNPore) surface is reported for chemoselective hydrogenation of C=C, C=C, C=N, and C=O bonds under mild conditions (8 atm H2 pressure, 90 °C). Silver doping in AuNPore, which was inevitable for its preparation through a process of dealloying of Au-Ag alloy, exhibited a remarkable difference in catalytic activity between two catalysts, Au>99Ag1NPore and Au90Ag10NPore.The former was more active and the latter less active in H2 hydrogenation, while the reverse tendency was observed for O2 oxidation. This marked contrast between H2 reduction and O2 oxidation is discussed. Further, Au>99Ag1NPore showed a high chemoselectivity toward reduction of terminal alkynes in the presence of internal alkynes which was not achieved using supported gold nanoparticle catalysts and other previously known methods. Reductive amination, which has great significance in synthesis of amines due to its atom-economical nature, was also realized using Au>99Ag1NPore, and the Au>99Ag1NPore/H2 system showed a preference for the reduction of aldehydes in the presence of imines. In addition to this high chemoselectivity, easy recovery and high reusability of AuNPore make it a promising heterogeneous catalyst for hydrogenation reactions.
- Takale, Balaram S.,Feng, Xiujuan,Lu, Ye,Bao, Ming,Jin, Tienan,Minato, Taketoshi,Yamamoto, Yoshinori
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p. 10356 - 10364
(2016/08/31)
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- Selective catalytic Hofmann: N -alkylation of poor nucleophilic amines and amides with catalytic amounts of alkyl halides
-
Using only catalytic amounts of alkyl halides in the reactions of poor nucleophilic amines/amides and alcohols led to a selective Hofmann N-alkylation reaction catalytic in alkyl halides, providing a practical and efficient method for the practical synthesis of mono- or di-alkylated amines/amides in high selectivities. This new method avoids the use of large amounts of bases, alkyl halides, and solvents, and generates water as the only byproduct. Preliminary mechanistic studies showed that alkyl halides are key intermediates/catalysts regeneratable in the reaction cycle.
- Xu, Qing,Xie, Huamei,Zhang, Er-Lei,Ma, Xiantao,Chen, Jianhui,Yu, Xiao-Chun,Li, Huan
-
supporting information
p. 3940 - 3944
(2016/07/21)
-
- Silica-Supported Oligomeric Benzyl Phosphate (Si-OBP) and Triazole Phosphate (Si-OTP) Alkylating Reagents
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The syntheses of silica-supported oligomeric benzyl phosphates (Si-OBPn) and triazole phosphates (Si-OTPn) using ring-opening metathesis polymerization (ROMP) for use as efficient alkylating reagents is reported. Ease of synthesis and grafting onto the surface of norbornenyl-tagged (Nb-tagged) silica particles has been demonstrated for benzyl phosphate and triazole phosphate monomers. It is shown that these silica polymer hybrid reagents, Si-OBPn and Si-OTPn, can be used to carry out alkylation reactions with an array of different nucleophiles to afford the corresponding benzylated and (triazolyl)methylated products in good yield and high purity.
- Maity, Pradip K.,Faisal, Saqib,Rolfe, Alan,Stoianova, Diana,Hanson, Paul R.
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p. 9942 - 9950
(2015/11/03)
-
- Construction of pyrrolophenanthridinone scaffolds mediated by samarium(II) diiodide and access to natural product synthesis
-
Pyrrolophenanthridinone derivatives including the natural products were readily synthesized by samarium(II)-mediated reductive cyclization of aryl radical onto a benzene ring under mild reaction conditions. This methodology was applied to the concise synt
- Suzuki, Kenji,Iwasaki, Hiroki,Domasu, Reika,Hitotsuyanagi, Naho,Wakizaka, Yuka,Tominaga, Mao,Kojima, Naoto,Ozeki, Minoru,Yamashita, Masayuki
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p. 5513 - 5519
(2015/08/03)
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- Palladium-catalyzed intramolecular reductive cross-coupling of Csp 2-Csp3 bond formation
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A Pd-catalyzed efficient reductive cross-coupling reaction without metallic reductant to construct a Csp2-Csp3 bond has been reported. A PdIV complex was proposed to be a key intermediate, which subsequently went through d
- Liu, Hui,Wei, Jianpeng,Qiao, Zongjun,Fu, Yana,Jiang, Xuefeng
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p. 8308 - 8313
(2014/07/08)
-
- Photoredox α-vinylation of α-amino acids and N -aryl amines
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A new coupling protocol has been developed that allows the union of vinyl sulfones with photoredox-generated α-amino radicals to provide allylic amines of broad diversity. Direct C-H vinylations of N-aryl tertiary amines, as well as decarboxylative vinylations of N-Boc α-amino acids, proceed in high yield and with excellent olefin geometry control. The utility of this new allyl amine forming reaction has been demonstrated via the syntheses of several natural products and a number of established pharmacophores.
- Noble, Adam,MacMillan, David W. C.
-
supporting information
p. 11602 - 11605
(2014/11/08)
-
- N-fused indolines through non-carbonyl-stabilized rhodium carbenoid C-H insertion of N-aziridinyl imines
-
Under rhodium catalysis, N-aziridinyl imines provided access to N-fused indolines through non-carbonyl-stabilized rhodium carbenoid C-H insertion. The utility of this methodology for the synthesis of architecturally complex heterocycles was further demonstrated by an expedient total synthesis of ( ±)-cryptaustoline (see scheme). Copyright
- Mahoney, Stuart J.,Fillion, Eric
-
supporting information; experimental part
p. 68 - 71
(2012/02/04)
-
- ROMP-derived oligomeric phosphates for application in facile benzylation
-
The development of new ROMP-based oligomeric benzyl phosphates (OBP n) is reported for use as soluble, stable benzylating reagents. These oligomeric reagents are readily synthesized from commercially available materials and conveniently polymerized and purified in a one-pot process, affording bench-stable, pure white, free-flowing solids on multigram scale. Utilization in benzylation reactions with a variety of nucleophiles is reported.
- Long, Toby R.,Maity, Pradip K.,Samarakoon, Thiwanka B.,Hanson, Paul R.
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supporting information; experimental part
p. 2904 - 2907
(2010/09/30)
-
- An expedient three-component synthesis of tertiary benzylamines
-
A Mannich-like zinc-mediated three-component reaction of aromatic halides, amines, and paraformaldehyde is described. This procedure, which involves the in situ formation of arylzinc reagents, allows the straightforward synthesis of a range of functionalized tertiary benzylamines. Georg Thieme Verlag Stuttgart.
- Le Gall, Erwan,Decompte, Alexandre,Martens, Thierry,Troupel, Michel
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experimental part
p. 249 - 254
(2010/04/05)
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- Highly chemoselective metal-free reduction of tertiary amides
-
This communication describes the chemoselective metal-free reduction of tertiary amides to the corresponding amines. Hantzsch ester is used as a mild reducing agent for the reduction of trifluoromethanesulfonic anhydride activated amides providing the tertiary amines with high functional group tolerance. Copyright
- Barbe, Guillaume,Charette, Andre B.
-
-
- A mild inter- and intramolecular amination of aryl halides with a combination of CuI and CsOAc
-
A unique combination of CuI and CsOAc was found to catalyze aryl amination under mild conditions. The reaction takes place at room temperature or at 90 °C with broad functional group compatibility. The intramolecular reaction was able to form five-, six-, and seven-membered rings with various protecting groups on the nitrogen atom. The scope of the intermolecular amination, as well as its applications to unsymmetrical N,N′-dialkylated phenylenediamines, was investigated.
- Kubo, Tetsuji,Katoh, Chiharu,Yamada, Ken,Okano, Kentaro,Tokuyama, Hidetoshi,Fukuyama, Tohru
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supporting information; experimental part
p. 11230 - 11236
(2009/04/11)
-
- Oligomeric benzylsulfonium salts: Facile benzylation via high-load ROMP reagents
-
(Chemical Equation Presented) The development of high-load, oligomeric benzylsulfonium salts, generated via ring-opening metathesis polymerization, and their utility in facile benzylations of various nucleophiles is reported. These oligomeric sulfonium salts exist as free-flowing powders and are stable at room temperature. After the benzylation event, purification is attained via simple dry load/filtration, followed by solvent removal to deliver products in excellent yield and purity.
- Zhang, Mianji,Flynn, Daniel L.,Hanson, Paul R.
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p. 3194 - 3198
(2008/02/04)
-
- Palladium-catalyzed reduction of N-(tert-Butoxycarbonyl)indoles by polymethylhydrosiloxane
-
The palladium-catalyzed [10% Pd(OH)2/C] reduction of N-(tert-butoxycarbonyl)indoles to the corresponding N-(tert-butoxycarbonyl) indolines is described. Polymethylhydrosiloxane was used as reducing agent and the reaction proceeded smoothly at r
- Chandrasekhar, Srivari,Basu, Debjit,Reddy, Ch. Raji
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p. 1509 - 1512
(2008/02/05)
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- Indolyl derivatives as liver-X-receptor (LXR) modulators
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The invention relates to compounds of formula (I): and pharmaceutically acceptable salts and pharmaceutically acceptable esters thereof, wherein R1, R2, R3, R4, R5, R6, A, m, n and p are defined as in claim 1. These compounds can be used as pharmaceutical compositions for the treatment of, for example, diabetes.
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Page/Page column 18
(2008/06/13)
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- Development of high-load, soluble oligomeric sulfonate esters via ROM polymerization: Application to the benzylation of amines
-
The development of high-load, soluble oligomeric sulfonate esters, generated via ROM polymerization, and their utility in the facile benzylation of an array of amines is reported. These polymeric sulfonate esters exist as free-flowing powders, are stable
- Zhang, Mianji,Moore, Joel D.,Flynn, Daniel L.,Hanson, Paul R.
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p. 2657 - 2660
(2007/10/03)
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- Concise synthesis of pyrrolophenanthridine alkaloids using a Pd-mediated biaryl coupling reaction with regioselective C-H activation via the intramolecular coordination of the amine to Pd
-
The concise synthesis of Amaryllidaceae alkaloids, such as anhydrolycorinone, anhydrolycorin-7-one, assoanine, and oxoassoanine, which have a pyrrolophenanthridine skeleton, was achieved in moderate yield using the Pd-mediated biaryl coupling reaction of
- Harayama, Takashi,Hori, Akihiro,Abe, Hitoshi,Takeuchi, Yasuo
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p. 1611 - 1616
(2007/10/03)
-
- Synthesis of Medium Ring Nitrogen Heterocycles via a Tandem Copper-Catalyzed C-N Bond Formation-Ring-Expansion Process
-
A simple method for the preparation of medium ring heterocycles (7-, 8-, 9-, and 10-membered) has been developed. The process employs a Cu-catalyzed coupling of a β-lactam with an aryl bromide or iodide followed by intramolecular attack of a pendant amino group. In some instances, the intermediate β-lactam is observable but can be converted to the aza-heterocycle by catalysis. Acetic acid was found to be superior to transition metal complexes as a catalyst for this ring-expansion process.
- Klapars, Artis,Parris, Sean,Anderson, Kevin W.,Buchwald, Stephen L.
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p. 3529 - 3533
(2007/10/03)
-
- Efficient heterogeneous oxidation of alkylarenes with molecular oxygen
-
(Chemical Equation Presented) Ru(OH)x/Al2O 3 efficiently catalyzes the heterogeneous aerobic oxygenation or oxidative dehydrogenation of alkylarenes to give the corresponding oxygenated or dehydrogenated products. Catalyst/product separation is very easy, and the recovered catalyst is reusable with retention of the high catalytic performance.
- Kamata, Keigo,Kasai, Jun,Yamaguchi, Kazuya,Mizuno, Noritaka
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p. 3577 - 3580
(2007/10/03)
-
- Free radical-mediated aryl amination and its use in a convergent [3 + 2] strategy for enantioselective indoline α-amino acid synthesis
-
The scope of aryl radical additions to the nitrogen of azomethines is described. Aryl, trifluoromethyl alkyl, and α,β-unsaturated ketimines engage in regioselective aryl-nitrogen bond formation via 5-exo cyclizations of an aryl radical to azomethine nitrogen. Selectivity for carbon-nitrogen over carbon-carbon bond formation is generally high (>95:5) and competes only with direct aryl radical reduction by stannane (0-10%). α-Ketoimines are a promising new class of carbon radical acceptors for which no competitive aryl radical reduction is observed. The reaction conditions are pH-neutral and are therefore among the mildest methods available for amination of an aromatic ring. The ketimines examined did not suffer from competitive reduction by stannane, offering an advantage over the use of diazo and azide functional groups as nitrogen sources for carbon radicals. The free radical-mediated aryl amination was sequenced with the O'Donnell phase transfer-catalyzed enantioselective alkylation strategy of glycinyl imine to provide either enantiomer of indoline α-amino acids with high ee. These new constrained phenyl alanine derivatives are now readily available for evaluation across a variety of applications.
- Viswanathan, Rajesh,Prabhakaran, Erode N.,Plotkin, Michael A.,Johnston, Jeffrey N.
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p. 163 - 168
(2007/10/03)
-
- Efficient nickel-mediated intramolecular amination of aryl chlorides
-
(Matrix presented) The use of an in situ generated Ni(0) catalyst associated with 2,2′-bipyridine or N,N′ -bis(2,6-diisopropylphenyl)dihydroimidazol-2-ylidene (SIPr) as a ligand and NaO-t-Bu as the base for the intramolecular coupling of aryl chlorides with amines is described. The procedure has been applied to the formation of five-, six-, and seven-membered rings.
- Omar-Amrani, Rafik,Thomas, Antoine,Brenner, Eric,Schneider, Raphael,Fort, Yves
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p. 2311 - 2314
(2007/10/03)
-
- Pyrrolo[2.1-a]isoquinoline derivatives
-
The present invention relates to pyrrolo[2.1-a]isoquinolines which are inhibitors of phosphodiesterase 10a, a process for preparing these compounds and a method of treating cancer in humans and animals by administering these compounds.
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-
-
- A mild copper-mediated intramolecular amination of aryl halides
-
A unique combination of copper iodide and cesium acetate was found to mediate intramolecular amination of aryl halides under mild conditions. The reaction proceeds at room temperature with primary or N-benzyl amines and at moderately elevated temperatures with other amine derivatives. The reaction has been applied to the formation of 5-, 6-, and 7-membered rings. Remarkably, halogens at the meta-position were retained, providing a definitive advantage over palladium-catalyzed systems.
- Yamada, Ken,Kubo, Tetsuji,Tokuyama, Hidetoshi,Fukuyama, Tohru
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p. 231 - 234
(2007/10/03)
-
- Synthesis of 2,3-dihydroindoles, indoles, and anilines by transition metal-free amination of aryl chlorides
-
Aliphatic and aromatic amines react with 2- and 3-chlorostyrene in the presence of potassium tert-butoxide to give N-substituted 2,3-dihydroindoles in good yields. The combination of this domino-amination protocol with a suitable dehydrogenation reaction gives access to pharmacologically interesting indoles in a one-pot procedure. Overall product yields of N-substituted indoles > 50% are obtained by this method starting from commercially available substrates. In addition to the intramolecular base-promoted amination of aromatic C-Cl, bonds, metal-free intermolecular aminations of aryl chlorides with primary and secondary amines are described. The use of potassium tert-butoxide as base allows the synthesis of various anilines in good to excellent yields. Due to the formation of aryne intermediates, either N-substituted anilines or meta-substituted anilines are produced with excellent selectivities.
- Beller,Breindl,Riermeier,Tillack
-
p. 1403 - 1412
(2007/10/03)
-
- N-Alkylation of anilines, carboxamides and several nitrogen heterocycles using CsF-Celite/alkyl halides/CH3CN combination
-
It has been found that the N-alkylation of aniline, carboxamides and heterocyclic compounds bearing an acidic hydrogen atom attached to nitrogen can be accomplished with alkyl halides in acetonitrile and cesium fluoride-celite employed as a solid base. In this manner, pyrrole, indole, pyrazole, imidazole, benzimidazole, carbazole, phthalimide, indazole, indoline, 2-pyrrolidinone, piperidine and 1,2,4-triazole can be successfully alkylated. The procedure is convenient, efficient and generally gives rise to the N-alkylated product exclusively.
- Hayat, Safdar,Atta-Ur-Rahman,Iqbal Choudhary,Khan, Khalid Mohammed,Schumann, Wilhelm,Bayer, Ernst
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p. 9951 - 9957
(2007/10/03)
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- Synthesis of (S)-proline derivatives with an alkylated N-benzyl substituent. Benzylation of (S)-indoline-2-carboxylic acid
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The synthesis is reported of (S)-proline derivatives which contain a 2,4,6-trimethyl-, 4-tert-butyl-, or pentamethylbenzyl substituent on the nitrogen atom. Under similar conditions the benzylation of indoline-2-carboxylic acid was unsuccessful. Treatment
- Popkov
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p. 544 - 547
(2007/10/03)
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- Process for producing 5-methylindolines
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Presentation of a method for producing a 5-methylindoline represented by the formula: STR1 (wherein R is a hydrogen atom or a lower alkyl group), which comprises catalytically hydrogenating a 1-(substituted)benzyl-5-formylindoline represented by the formula: STR2 (wherein R1 is a hydrogen atom or a lower alkyl group, and R2 is a hydrogen atom, a lower alkyl group or a lower alkoxy group) in the presence of an inert solvent and a palladium catalyst.
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- Preparation of arylamines
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A method of preparing an arylamine compound includes reacting a metal amide comprising a metal selected from the group consisting of tin, boron, zinc, magnesium, indium and silicon, with an aromatic compound comprising an activated substituent in the pres
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- Intramolecular palladium-catalyzed aryl amination and aryl amidation
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Upon treatment with a palladium catalyst and a suitable base, aromatic halides undergo intramolecular substitution to form five, six, and seven-membered rings. In a similar fashion aryl halides with pendant amides or sulfonamides are cyclized to form five and six-membered rings.
- Wolfe, John P.,Rennels, Roger A.,Buchwald, Stephen L.
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p. 7525 - 7546
(2007/10/03)
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- Eine einfache katalytische Methode zur Synthese von Arylaminen aus Arylbromid
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Stichworte: Arylamine / Indoline / Palladiumverbindungen / Katalyse
- Guram, Anil S.,Rennels, Roger A.,Buchwald, Stephen L.
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p. 1456 - 1459
(2007/10/02)
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- Free-Radical Chemistry of Imines
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Aryl radicals bearing an aldimino functional group as part of an ortho substituent cyclized by addition to C and/or N of the imino group.When the choice was between 5-exo closure to C and 6-endo closure to N, the former predominated.However, 6-endo closure to C predominated over 5-exo cyclization to N in isomeric imines.Absolute values of cyclization rate constants were determined and an explanation for the unusual 6-endo preference is offered.Chiral induction in 6-endo cyclization to C of an aldimine from D-glyceraldehyde acetonide was observed, and its sense was determined.
- Tomaszewski, Miroslaw J.,Warkentin, John,Werstiuk, Nick H.
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p. 291 - 322
(2007/10/02)
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- Direct Substitution of Aromatic Ethers by Lithium Amides. A New Aromatic Amination Reaction
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Reaction of lithiated dialkylamines with methoxy aromatics in refluxing THF leads to products resulting from a direct ipso-substitution.Especially with lithiated secondary amines high conversions and selectivities are achieved.Sulfonyl-substituted aromatics react equally well, but halogenated aromatics give rise to side-products arising from a competing pathway via aryne intermediates.The scope and mechanistic implications of this novel nucleophilic amination reaction are described.
- Hoeve, Wolter ten,Kruse, Chris, G.,Luteyn, Jan M.,Thiecke, Janet R. G.,Wynberg, Hans
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p. 5101 - 5106
(2007/10/02)
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