- Synthesis of DPA-triazole structures and their application as ligand for metal catalyzed organic reactions
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In this work, the use of DPA-triazole (DPA = dipicolylamine) molecules as ligands for metal catalyzed organic reactions has been investigated. A small library of ligands has been prepared by a CuAAC (click reaction) between propargyl-DPA and different azi
- Colombo Dugoni, Greta,Sacchetti, Alessandro,Urra Mancilla, Carolina
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- One-Pot Enzyme Cascade Catalyzed Asymmetrization of Primary Alcohols: Synthesis of Enantiocomplementary Chiral β-Nitroalcohols
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Biocatalytic asymmetrization of inexpensive and stable primary alcohols to prepare enantioenriched β-nitroalcohols is an important development in green chemistry for the production of chiral pharmaceutical intermediates. Herein, we report a one-pot, two-step cascade reaction sequence in which first benzylic alcohols were oxidized to produce corresponding benzaldehydes using horse liver alcohol dehydrogenase (HLADH). The in situ generated aldehydes were then reacted in a biphasic medium with nitromethane by Arabidopsis thaliana hydroxynitrile lyase (AtHNL) or Baliospermum montanum HNL (BmHNL) catalyzed Henry reaction to produce stereoselective β-nitroalcohols with (R) or (S) configuration, respectively. Using HLADH-AtHNL, (R)-β-nitroalcohols were obtained in up to 64% conversion, and HLADH-BmHNL, (S)-β-nitroalcohols in up to 70% conversion, while in both cases excellent stereoselectivity (up to >99% ee) was achieved. The concept was proven by functionalization of sp3 C?H bond of ten simple achiral benzylic alcohols to enantiocomplementary chiral β-nitroalcohols. (Figure presented.).
- Chatterjee, Ayon,Kumar Padhi, Santosh,Rao, D. H. Sreenivasa
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supporting information
p. 5310 - 5318
(2021/10/02)
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- Ketoreductase catalyzed stereoselective bioreduction of α-nitro ketones
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We report here the stereoselective bioreduction of α-nitro ketones catalyzed by ketoreductases (KREDs) with publicly known sequences. YGL039w and RasADH/SyADH were able to reduce 23 class I substrates (1-aryl-2-nitro-1-ethanone (1)) and ten class II substrates (1-aryloxy-3-nitro-2-propanone (4)) to furnish both enantiomers of the corresponding β-nitro alcohols, with good-to-excellent conversions (up to >99%) and enantioselectivities (up to >99% ee) being achieved in most cases. To the best of our knowledge, KRED-mediated reduction of class II α-nitro ketones (1-aryloxy-3-nitro-2-propanone (4)) is unprecedented. Select β-nitro alcohols, including the synthetic intermediates of bioactive molecules (R)-tembamide, (S)-tembamide, (S)-moprolol, (S)-toliprolol and (S)-propanolol, were stereoselectively synthesized in preparative scale with 42% to 90% isolated yields, showcasing the practical potential of our developed system in organic synthesis. Finally, the advantage of using KREDs with known sequence was demonstrated by whole-cell catalysis, in which β-nitro alcohol (R)-2k, the key synthetic intermediate of hypoglycemic natural product (R)-tembamide, was produced in a space-time yield of 178 g L?1 d?1 as well as 95% ee by employing the whole cells of a recombinant E. coli strain coexpressing RasADH and glucose dehydrogenase as the biocatalyst.
- Wang, Zexu,Wu, Xiaofan,Li, Zhining,Huang, Zedu,Chen, Fener
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supporting information
p. 3575 - 3580
(2019/04/14)
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- Organocatalytic asymmetric Michael/hemiacetalization/acyl transfer reaction of α-nitroketones with o-hydroxycinnamaldehydes: Synthesis of 2,4-disubstituted chromans
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An organocatalytic asymmetric cascade Michael/hemiketalization/acyl transfer reaction between o-hydroxycinnamaldehydes and α-nitroketones is developed. Prolinol TMS ether catalyst in combination with benzoic acid was found to be the most effective for this reaction which proceeds through an equilibrium of lactols to provide a single diastereomer of enantiopure 2,4-disubstituted chromans.
- Maity, Rajendra,Pan, Subhas Chandra
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supporting information
p. 1598 - 1608
(2018/03/08)
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- Organocatalytic Asymmetric Domino Michael/Acyl Transfer Reaction Between α-Nitroketones and in situ-Generated ortho-Quinone Methides: Route to 2-(1-Arylethyl)phenols
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An organocatalytic asymmetric domino Michael/acyl transfer reaction between α-nitroketones and o-quinone methides is disclosed. o-Quinone methides are generated in situ from 2-sulfonylmethylphenols in basic medium. With 10 mol% of bifunctional squaramide catalyst, high yields and excellent enantioselectivities are achieved for a variety of O-acyl 2-(1-arylethyl)phenols under mild reaction condition. (Figure presented.).
- Gharui, Chandan,Behera, Debasmita,Pan, Subhas Chandra
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supporting information
p. 4502 - 4508
(2018/11/10)
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- Keratin protein-catalyzed nitroaldol (henry) reaction and comparison with other biopolymers
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Here we describe a preliminary investigation on the ability of natural keratin to catalyze the nitroaldol (Henry) reaction between aldehydes and nitroalkanes. Both aromatic and heteroaromatic aldehydes bearing strong or moderate electron-withdrawing group
- H?ring, Marleen,Pettignano, Asja,Quignard, Fran?oise,Tanchoux, Nathalie,Díaz, David Díaz
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- Selective synthesis of nitroalcohols in the presence of Ambersep 900 OH as heterogeneous catalyst
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Abstract A green protocol has been developed for the selective synthesis of β-nitroalcohols using commercially available Ambersep 900 OH as reusable heterogeneous catalyst. The reaction between aldehyde and nitromethane was performed under solvent-free condition at room temperature within a short time (70-150 min) in the presence of 10 wt % of Ambersep 900 OH to produce corresponding nitroalcohols in high yield (72-91 %). After the reaction is over, the catalyst can be separated and reused (3 cycles) without appreciable loss in its activity.
- Lodh, Rajsekhar,Sarma, Manas Jyoti,Borah, Arun Jyoti,Phukan, Prodeep
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p. 969 - 972
(2015/02/19)
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- Urea-pyridine bridged periodic mesoporous organosilica: An efficient hydrogen-bond donating heterogeneous organocatalyst for Henry reaction
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Hydrogen-bond donating (HBD) organocatalysts have been employed as an important class of catalysts for the activation of small molecules. However, the use of these catalysts was restricted on account of the self-aggregation of HBD-active species. In this work, a successful approach was developed to construct novel urea-pyridine bridged periodic mesoporous organosilica (PMO) to prevent the unwanted self-recognition and aggregation of urea-based catalytic center by spatial isolation, unleashing its HBD organocatalytic activity along with cooperative effect from the pyridine unit for efficient Henry reaction. The urea-pyridine bridged PMO catalyst presents high structural stability and high catalytic recyclability.
- Borah, Parijat,Mondal, John,Zhao, Yanli
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p. 129 - 134
(2015/08/06)
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- Merging Asymmetric Henry Reaction with Organocatalytic Cascade Reaction for the Construction of a Chiral Indolizidine Alkaloid Skeleton
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A sequential reaction combining the copper-catalyzed asymmetric Henry reaction with the organocatalytic Michael addition-hemiacetalization cascade reaction was developed. The C1-symmetric chiral diamine L1-copper complex was responsible for the first highly enantioselective Henry reaction, while diphenylprolinol silyl ether A acted as effective organocatalyst for the second cascade reaction between chiral β-nitro alcohol and α,β-unsaturated aldehydes. Via rational design and combination of the two independent catalytic systems, good yields and excellent enantioselectivities and diastereoselectivities were achieved for a broad substrate scope under mild reaction conditions. The synthetic utility of this sequential catalytic asymmetric cascade reaction was demonstrated as an alternative and straightforward stereoselective synthesis strategy for chiral indolizidine alkaloid and its analogues.
- Zhou, Yirong,Yang, Qin,Shen, Jian,Chen, Xin,Peng, Yiyuan,Gong, Yuefa
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p. 1446 - 1456
(2015/02/19)
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- Design aspects of metal-free nitrogen-based catalysts and their influence on the yield in the Henry reaction
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Design aspects of metal-free nitrogen-based catalysts and their influence on the yield in the Henry reaction are disclosed. C 1-Symmetric, N,N-1,2-disposed amine-imine type catalysts were found to be most efficient. C 1-N,N-1,2-Disposed 1,2,3,4-tetrahydro-1,1′-biisoquinoline selectively and efficiently catalyzed the addition of nitromethane to α-keto esters and aldehydes giving exclusively the corresponding β-nitro alcohol adducts in excellent yields under very mild conditions. Georg Thieme Verlag Stuttgart New York.
- Yao, Qiong Ji,Khong, Duc Thinh,Gao, Qi,Judeh, Zaher M. A.
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p. 1793 - 1801
(2014/07/08)
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- (2S,5R)-2-Methylaminomethyl-1-methyl-5-phenylpyrrolidine, a chiral diamine ligand for copper(ii)-catalysed Henry reactions with superb enantiocontrol
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A cis-2-aminomethyl-5-phenylpyrrolidine, which is easily available from methyl Boc-l-pyroglutamate, was found to be a highly efficient chiral ligand for Cu(ii)-catalysed Henry reactions. Excellent yields (>90%) and superb levels of enantiocontrol (98.5-99.6% ee) were reached with aromatic, heteroaromatic, vinylic, and aliphatic aldehydes (36 examples). This journal is the Partner Organisations 2014.
- Scharnagel, Dagmar,Prause, Felix,Kaldun, Johannes,Haase, Robert G.,Breuning, Matthias
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supporting information
p. 6623 - 6625
(2014/06/10)
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- The henry reaction in [Bmim][PF6]-based microemulsions promoted by acylase
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An environmentally-friendly, enzyme-promoted procedure for the Henry reaction was first studied using water-in-[Bmim][PF6] microemulsions as reaction medium. The Amano acylase from Aspergillus oryzae showed better catalytic activity for the addition reactions of nitromethane with a series of aromatic aldehydes, and a highest yield of 90% was obtained.
- Xia, Wen-Jian,Xie, Zong-Bo,Jiang, Guo-Fang,Le, Zhang-Gao
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p. 13910 - 13919
(2014/01/06)
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- Highly efficient and large-scalable glucoamylase-catalyzed Henry reactions
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Eco-friendly, highly efficient and large-scalable Henry reactions of aromatic aldehydes and nitroalkanes catalyzed by glucoamylase from Aspergillus niger (AnGA) are described. The reactions were carried out at 30 °C in the mixed solvents of ethanol and wa
- Gao, Na,Chen, Yan-Li,He, Yan-Hong,Guan, Zhi
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p. 16850 - 16856
(2013/09/23)
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- Rhodium-catalyzed enantioselective hydrogenation of β-acylamino nitroolefins: A new approach to chiral β-amino nitroalkanes
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An efficient and highly enantioselective catalytic asymmetric hydrogenation of β-acylamino nitroolefins has been realized by using Rh-TangPhos as the catalyst. A series of β-amino nitroalkane products, which are versatile intermediates in organic synthesis, were obtained with high yield and good enantioselectivity.
- Zhou, Ming,Dong, Dejun,Zhu, Baolin,Geng, Huiling,Wang, Yan,Zhang, Xumu
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supporting information
p. 5524 - 5527
(2013/11/19)
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- Asymmetric Henry reaction catalyzed by Cu(I)-based chiral amino alcohol complex
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The Cu(I)-based complex prepared from (S)-2-(furan-2-yl-methylamino)-2- phenylethanol (5c) and CuCl was used as catalyst in enantioselective Henry reactions of arylaldehydes and nitromethane, which gave 89% ee and 95% yield at ambient temperature. The proposed catalytic cycle of an asymmetric Henry reaction was suggested. TUeBITAK.
- Shen, Tianhua,Qin, Quan,Ni, Hang,Xia, Ting,Zhou, Xiaocong,Cui, Funa,Li, Junqi,Ran, Deqiang,Song, Qingbao
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p. 966 - 977
(2013/12/04)
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- Mn(OAc)2/Schiff base as a new efficient catalyst system for the Henry reaction of nitroalkanes with aldehydes
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A series of novel Schiff bases bearing triazole structure were synthesized and characterized by IR and NMR. Mn(OAc)2/Schiff base efficiently catalyzed Henry reaction of nitroalkanes with aldehydes to produce the corresponding products of β-nitroalcohols, under mild conditions with high yields (up to 99%). A reaction mechanism is proposed based on the experimental results.
- Zhou, Guang Peng,Hui, Yong Hai,Wan, Ning Ning,Liu, Qiu Ju,Xie, Zheng Feng,De Wang, Ji
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scheme or table
p. 690 - 694
(2012/07/03)
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- Highly enantioselective reduction of β-amino nitroolefins with a simple n-sulfinyl urea as bifunctional catalyst
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Simple but effective: A structurally simple N-sulfinyl urea was found to be a highly efficient bifunctional catalyst, which allows for the development of a novel pathway for the construction of chiral β-amino nitroalkanes through enantioselective reduction of β-amino nitroolefins by trichlorosilane. High yields and excellent enantioselectivities were obtained for a broad range of β-arylamino nitroolefin substrates (see scheme). Copyright
- Liu, Xiang-Wei,Yan, Yan,Wang, Yong-Qiang,Wang, Chao,Sun, Jian
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supporting information; experimental part
p. 9204 - 9207
(2012/08/27)
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- Copper complex of aminoisoborneol schiff base Cu2(SBAIB-d) 2: An efficient catalyst for direct catalytic asymmetric nitroaldol (henry) reaction
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A new bifunctional copper complex of the aminoisoborneol Schiff base - Cu2(SBAIB-d)2 - has been developed for the effective direct catalytic asymmetric Henry reaction. One mol% of this catalyst produces the expected Henry products in high yields (up to 99%) with excellent enantioselectivities (up to 98% ee). The utility of the present catalyst was also extended to the Henry reaction with nitroethane and 1-nitropropane that furnished the corresponding products in moderate to high yields (up to 99%) with moderate to high enantioselectivities of syn (up to 98% ee) and anti (up to 98% ee) diastereomers. The highlights of this catalytic system are easy manipulation, air and moisture tolerance, the need for 1 mol% of an easily synthesizable catalyst and the high enantioselectivities achieved for a wide range of substrates. Copyright
- Boobalan, Ramalingam,Lee, Gene-Hsian,Chen, Chinpiao
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supporting information
p. 2511 - 2520
(2012/11/07)
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- Crown ether complex cation ionic liquids: Preparation and applications in organic reactions
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A series of crown ether complex cation ionic liquids (CECILs) were designed, synthesised and characterised by NMR spectroscopy, HRMS, thermogravimetric differential thermal analysis (TG-DTA) and elemental analysis. Their applications in various organic reactions were investigated: [15-C-5Na][OH], [15-C-5Na][OAc], [18-C-6K][OH] and [18-C-6K][OAc] (15-C-5=[15]crown-5; 18-C-6=[18]crown-6) efficiently catalysed the Michael addition of alkenes and relevant nucleophiles; [18-C-6K][OH] and [15-C-5Na][OH] effectively catalysed the Henry reaction of nitromethane and aromatic aldehydes; [18-C-6K][OH] has excellent catalytic efficiency for Knoevenagel condensation of aromatic aldehydes and malononitrile; PdCl2/[18-C-6K] 3[PO4]/K2CO3 efficaciously catalysed the Heck reaction of olefins and aromatic halides; [18-C-6K][BrO3] can be used as both oxidant and solvent in the oxidation reaction of aromatic alcohols. The CECIL catalysts [15-C-5Na][OH] (Michael addition) and [18-C-6K][OH] (Henry reaction) can be recycled and reused several times without obvious loss of activity and their recovery is very simple.
- Song, Yingying,Jing, Huanwang,Li, Bo,Bai, Dongsheng
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experimental part
p. 8731 - 8738
(2011/09/16)
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- Enzymatic synthesis of optical pure β-nitroalcohols by combining d-aminoacylase-catalyzed nitroaldol reaction and immobilized lipase PS-catalyzed kinetic resolution
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An enzymatic method which combines d-aminoacylase catalyzed nitroaldol reaction and lipase PS-IM catalyzed acyl resolution reaction was constructed to obtain optically pure β-nitroalcohols in organic media under mild conditions. A series of β-nitroalcohols were synthesized and then resolved, with excellent ee values (>95%) and yields mostly, giving enantiomerically pure acetate and alcohol of the opposite configuration simultaneously.
- Xu, Fan,Wang, Junliang,Liu, Bokai,Wu, Qi,Lin, Xianfu
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supporting information; experimental part
p. 2359 - 2361
(2011/10/19)
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- Enzyme-catalyzed Henry (nitroaldol) reaction
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Transglutaminase was first used to catalyze Henry reactions of aliphatic, aromatic and hetero-aromatic aldehydes with nitroalkanes. The reactions were carried out at room temperature, and the corresponding nitro alcohols were obtained in yields up to 96%.
- Tang, Rong-Chang,Guan, Zhi,He, Yan-Hong,Zhu, Wen
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experimental part
p. 62 - 67
(2010/10/04)
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- Investigation of DNA as a catalyst for Henry reaction in water
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Double-stranded DNA of natural origin can be used to facilitate nitro-aldol (or Henry) reaction in aqueous solution. The Royal Society of Chemistry.
- Fan, Jinmin,Sun, Gaojun,Wan, Changfeng,Wang, Zhiyong,Li, Yingfu
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scheme or table
p. 3792 - 3794
(2009/02/07)
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- Novel 1H-(benzimidazol-2-yl)-1H-pyridin-2-one inhibitors of insulin-like growth factor I (IGF-1R) kinase
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A novel class of 1H-(benzimidazol-2-yl)-1H-pyridin-2-one inhibitors of insulin-like growth factor I (IGF-1R) kinase is described. This report discusses the SAR of 4-(2-hydroxy-2-phenylethylamino)-substituted pyridones with improved IGF-1R potency.
- Wittman, Mark D.,Balasubramanian, Balu,Stoffan, Karen,Velaparthi, Upender,Liu, Pieying,Krishnanathan, Subramaniam,Carboni, Joan,Li, Aixin,Greer, Ann,Attar, Ricardo,Gottardis, Marco,Chang, Chiehying,Jacobson, Bruce,Sun, Yax,Hansel, Steven,Zoeckler, Mary,Vyas, Dolatrai M.
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p. 974 - 977
(2007/10/03)
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- Efficient nitro-aldol reaction using SmI2: A new route to nitro alcohols under very mild conditions
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(Chemical Equation Presented) A novel method to obtain racemic 1-nitroalkan-2-ols by reaction of bromonitromethane with a variety of aldehydes and promoted by SmI2 is reported. On the basis of these results, the chiral version has also been per
- Concellon, Jose M.,Rodriguez-Solla, Humberto,Concellon, Carmen
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p. 7919 - 7922
(2007/10/03)
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- Imidazole based kinase inhibitors
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The present invention provides compounds having Formula I and their use for the treatment of cancer.
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Page/Page column 8
(2008/06/13)
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- NOVEL TYROSINE KINASE INHIBITORS
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The present invention provides compounds of formula (I) and pharmaceutically acceptable salts thereof. The formula (I) compounds inhibit tyrosine kinase enzymes thereby making them useful as anti-cancer agents.
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- Novel tyrosine kinase inhibitors
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The present invention provides compounds of formula I and pharmaceutically acceptable salts thereof. The formula I compounds inhibit tyrosine kinase enzymes thereby making them useful as anti-cancer agents. The formula I compounds are also useful for the treatment of other diseases which can be treated by inhibiting tyrosine kinase enzymes.
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- Potassium Phosphate Catalyzed Nitroaldol Reaction
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Potassium phosphate was found to catalyze condensation of nitroalkanes with various aliphatic and aromatic aldehydes to form nitroaldols in excellent yields in acetonitrile medium at room temperature.
- Desai, Uday V.,Pore,Mane,Solabannavar,Wadgaonkar
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- A New and Efficient Synthesis of Pyrrolo[2,3-d]pyrimidine Anticancer Agents: Alimta (LY231514, MTA), Homo-Alimta, TNP-351, and Some Aryl 5-Substituted Pyrrolo[2,3-d]pyrimidines
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Alimta, as well as homo-Alimta, a nonbridged analogue of Alimta, and TNP-351 have been prepared by a new method that involves Michael addition of the appropriate 1-nitroalkene with 2,6-diamino-3H-pyrimidin-4-one or 2,4,6-triaminopyrimidine, followed by a Nef reaction of the resulting primary nitro Michael adduct. Spontaneous intramolecular cyclization of the resulting aldehyde with the pyrimidine 6-amino group yields the corresponding pyrrolo[2,3-d]pyrimidine. A series of previously unknown 5-arylpyrrolo[2,3-d]pyrimidines was prepared by the same methodology from the above pyrimidines and nitrostyrenes. It has been found that the intermediate primary nitro Michael adduct can be prepared in a single step by sonication of a mixture of an arylaldehyde, nitromethane, and the 6-aminopyrimidine in acetic acid containing ammonium acetate.
- Taylor, Edward C.,Liu, Bin
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p. 9938 - 9947
(2007/10/03)
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