cas 7345-79-1, 2-Bromocinnamic acid | Articles data

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Metal-Free Hydropyridylation of Thioester-Activated Alkenes via Electroreductive Radical Coupling
An electrochemical hydropyridylation of thioester-activated alkenes with 4-cyanopyridines has been developed. The reactions experience a tandem electroreduction of both substrates on the cathode surface, protonation, and radical cross-coupling process, resulting in a variety of valuable pyridine variants, which contain a tertiary and even a quaternary carbon at the α-position of pyridines, in high yields. The employment of thioesters to the conjugated alkenes enables no requirement of catalyst and high temperature, representing a highly sustainable synthetic method.
Xu, Hehuan,Liu, Jiayu,Nie, Feiyun,Zhao, Xiaowei,Jiang, Zhiyong
p. 16204 - 16212
(2021/10/25)

Design, Synthesis, and Anticancer Activity of Cinnamoylated Barbituric Acid Derivatives
This work deals with the design and synthesis of 18 barbituric acid derivatives bearing 1,3-dimethylbarbituric acid and cinnamic acid scaffolds to find potent anticancer agents. The target molecules were obtained through Knoevenagel condensation and acylation reaction. The cytotoxicity was assessed by the MTT assay. Flowcytometry was performed to determine the cell cycle arrest, apoptosis, ROS levels and the loss of MMP. The ratios of GSH/GSSG and the MDA levels were determined by using UV spectrophotometry. The results revealed that introducing substitutions (CF3, OCF3, F) on the meta- of the benzyl ring of barbituric acid derivatives led to a considerable increase in the antiproliferative activities compared with that of corresponding ortho- and para-substituted barbituric acid derivatives. Mechanism investigation implied that the 1c could increase the ROS and MDA level, decrease the ratio of GSH/GSSG and MMP, and lead to cell cycle arrest. Further research is needed for structural optimization to enhance hydrophilicity, thereby improve the biological activity of these compounds.
Li, Peng-Xiao,Liu, Guo-Yun,Liu, Ren-Min,Liu, Yue,Mu, Wen-Wen,Sun, Ya-Lei,Yang, Jie
(2022/01/13)

Iron-catalyzed domino decarboxylation-oxidation of α,β-unsaturated carboxylic acids enabled aldehyde C-H methylation
A practical and general iron-catalyzed domino decarboxylation-oxidation of α,β-unsaturated carboxylic acids enabling aldehyde C-H methylation for the synthesis of methyl ketones has been developed. This mild, operationally simple method uses ambient air as the sole oxidant and tolerates sensitive functional groups for the late-stage functionalization of complex natural-product-derived and polyfunctionalized molecules.
Gong, Pei-Xue,Xu, Fangning,Cheng, Lu,Gong, Xu,Zhang, Jie,Gu, Wei-Jin,Han, Wei
supporting information
p. 5905 - 5908
(2021/06/18)

Cinnamic acid derivative and preparation method and application thereof
The invention provides a cinnamic acid derivative. The cinnamic acid derivative is of the structure as shown in the formula I. The invention also provides two methods for preparing the cinnamic acid derivative. The two methods depend on a single bond or double bonds in the structure shown in the formula I. The invention further provides a pesticide. The pesticide comprises the cinnamic acid derivative. In addition, the invention provides a sterilization method. The sterilization method includes the step of applying the cinnamic acid derivative or the pesticide to crops. The crops include rice,wheat, fruit trees and vegetables. The low-toxicity, low-residue-content and high-activity environment-friendly cinnamic acid derivative is developed, and the cinnamic acid derivative pesticide can replace traditional high-toxicity and high-residue-content pesticides.
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Paragraph 0146-0148

(2019/10/22)

Enantioselective Synthesis of N?H-Free 1,5-Benzothiazepines
An enantioselective sulfa-Michael-cyclization reaction was developed for the synthesis of 1,5-benzothiazepines with versatile pharmacological activities. The reaction between 2-aminothiophenol and α,β-unsaturated pyrazoleamides gave direct access to N?H-free 1,5-benzothiazepines in the presence of a chiral N,N′-dioxide/Yb(OTf)3complex. Excellent enantioselectivities (up to 96 % ee) and high yields (up to 99 %) were obtained for a broad range of substrates under mild reaction conditions. This method provided a facile approach to the antidepressant drug (R)-(?)-Thiazesim.
Wang, Guojin,Tang, Yu,Zhang, Yu,Liu, Xiaohua,Lin, Lili,Feng, Xiaoming
supporting information
p. 554 - 557
(2017/01/18)

Carbene-catalyzed LUMO activation of alkyne esters for access to functional pyridines
A carbene-catalyzed LUMO activation of α,β-unsaturated alkyne esters is reported. This catalytic process allows for effective reactions of alkyne esters with enamides to synthesize functional pyridines via simple protocols. A previously unexplored unsaturated alkyne acyl azolium intermediate is involved in the key step of the reaction.
Mou, Chengli,Wu, Jichang,Huang, Zhijian,Sun, Jun,Jin, Zhichao,Chi, Yonggui Robin
p. 13359 - 13362
(2017/12/26)

Chiral phosphoric acid catalyzed enantioselective annulation of acyclic enecarbamates to: In situ -generated ortho -quinone methides
The first organocatalytic asymmetric reaction of acyclic enecarbamates with o-quinone methides is disclosed. BINOL-based phosphoric acid catalysts were found to be suitable for the annulation reaction. With 10 mol% of the TRIP catalyst, high yields as well as excellent diastereo- and enantioselectivities are achieved for a variety of 2,3,4-trisubstituted chroman products.
Gharui, Chandan,Singh, Shreya,Pan, Subhas Chandra
supporting information
p. 7272 - 7276
(2017/09/25)

Modular Construction of Fluoroarenes from a New Difluorinated Building Block by Cross-Coupling/Electrocyclisation/Dehydrofluorination Reactions
Palladium-catalysed coupling reactions based on a novel and easy-to-synthesise difluorinated organotrifluoroborate were used to assemble precursors to 6π-electrocyclisations of three different types. Electrocyclisations took place at temperatures between 90 and 240 °C, depending on the central component of the π-system; nonaromatic trienes were most reactive, but even systems that required the temporary dearomatisation of two arenyl subunits underwent electrocyclisation, albeit at elevated temperatures. Photochemical conditions were effective for these more demanding reactions. The package of methods delivered a structurally diverse set of fluorinated arenes, spanning a 20 kcal mol?1range of reactivity, by a flexible route.
Percy, Jonathan M.,Emerson, Helena,Fyfe, James W. B.,Kennedy, Alan R.,Maciuk, Sergej,Orr, David,Rathouská, Lucie,Redmond, Joanna M.,Wilson, Peter G.
supporting information
p. 12166 - 12175
(2016/08/16)

Telescopic one-pot condensation-hydroamination strategy for the synthesis of optically pure L-phenylalanines from benzaldehydes
A chemo-enzymatic telescopic approach was designed for the synthesis of L-arylalanines in high yield and optical purity, starting from commercially available and inexpensive substituted benzaldehydes. The method exploits a chemical Knoevenagel–Doebner condensation (optimised to give complete conversions in a short reaction time, employing microwave irradiation) and a biocatalytic phenylalanine ammonia lyase mediated hydroamination (for the stereoselective addition of ammonia). The two reactions can be run sequentially in one pot, bringing together the advantages of chemical and biological catalysis. The preparative applicability was demonstrated with the synthesis of five L-dihalophenylalanines (71–84% yield, 98–99% ee) of relevance as molecular probes, for medicinal chemistry and for the synthesis of pharmaceutical ingredients.
Parmeggiani, Fabio,Ahmed, Syed T.,Weise, Nicholas J.,Turner, Nicholas J.
p. 7256 - 7262
(2016/10/26)

Aromatic diacylhydrazine derivatives as a new class of polo-like kinase 1 (PLK1) inhibitors
A novel class of aromatic diacylhydrazine derivatives was designed as PLK1 inhibitors. All the 19 new synthesized compounds were assayed for antitumor activity against the respective cervical cancer cells. In which, nine compounds with better antitumor activities were further tested for their PLK1 inhibitory activity. Last, we have successfully found that compound 7k showed both the promising antitumor activity with IC50 of 0.17 μM against the cervical cancer cells, and also processed the most potent PLK1 inhibitory activity with IC50 of 0.03 μM. In addition, docking simulation also carried out in this study to give a potent prediction binding mode between the small molecule and PKL1 (PDB code: 1umw) protein.
Sun, Juan,Lv, Peng-Cheng,Guo, Feng-Jiao,Wang, Xin-Yi,Han, Xiao-,Zhang, Yang,Sheng, Gui-Hua,Qian, Shao-Song,Zhu, Hai-Liang
p. 420 - 426
(2014/06/09)

Synthesis of substituted nitroolefins: A copper catalyzed nitrodecarboxylation of unsaturated carboxylic acids
A novel, mild and convenient method for the nitrodecarboxylation of substituted cinnamic acid derivatives to their nitroolefins is achieved using a catalytic amount of CuCl (10 mol%) and tert-butyl nitrite (2 equiv.) as a nitrating agent in the presence of air. This reaction provides a useful method for the synthesis of β,β-disubstituted nitroolefin derivatives, which are generally difficult to access from other conventional methods. Additionally, this reaction is selective as the E-isomer of the acid derivatives furnishes the corresponding E-nitroolefins. One more salient feature of the method is, unlike other methods, no metal nitrates or HNO3 are employed for the transformation.
Rokade, Balaji V.,Prabhu, Kandikere Ramaiah
supporting information
p. 6713 - 6716
(2013/10/01)

Synthesis and antitumor activity of 1,3,4-oxadiazole possessing 1,4-benzodioxan moiety as a novel class of potent methionine aminopeptidase type II inhibitors
A series of 1,3,4-oxadiazole derivatives containing 1,4-benzodioxan moiety (7a-7q) have been designed, synthesized and evaluated for their antitumor activity. Most of the synthesized compounds were proved to have potent antitumor activity and low toxicity. Among them, compound 7a showed the most potent biological activity against Human Umbilical Vein Endothelial cells, which was comparable to the positive control. The results of apoptosis and flow cytometry (FCM) demonstrated that compound 7a induce cell apoptosis by the inhibition of MetAP2 pathway. Molecular docking was performed to position compound 7a into MetAP2 binding site in order to explore the potential target.
Sun, Juan,Li, Ming-Hui,Qian, Shao-Song,Guo, Feng-Jiao,Dang, Xiao-Fang,Wang, Xiao-Ming,Xue, Ya-Rong,Zhu, Hai-Liang
supporting information
p. 2876 - 2879
(2013/06/26)

A practical and convenient protocol for the synthesis of (E)-α,β-unsaturated acids
α,β-Unsaturated acids are very useful and versatile reagents in organic synthesis. A novel, practical, and convenient catalytic protocol comprising FeCl3·6H2O (0.5 mol %) and H 2O (1 equiv) in CH3NO2 is described for the rapid synthesis of α,β-unsaturated acids with high E-stereoselectivity under both microwave and conventional heating conditions with high TON and TOF values. This powerful approach efficiently demonstrated the utility of biomass derived aldehydes to build chemical agents used as fuel additives. The method proved to be scalable to gram scale synthesis.
Mohite, Amar R.,Bhat, Ramakrishna G.
p. 4564 - 4567
(2013/09/24)

Lyaseenzymes, Nucleic Acids Encoding Them and Methods For Making and Using Them
This invention provides polypeptides having lyase activity, polynucleotides encoding these polypeptides, and meth-°ds of making and using these polynucleotides and polypeptides. In one aspect, the invention is directed to polypeptides having ammonia lyase activity, e.g., phenylalanine ammonia lyase, tyrosine ammonia lyase and/or histidine ammonia lyase activity, including thermostable and thermotolerant activity, and polynucleotides encoding these enzymes, and making and using these polynucleotides and polypeptides. The polypeptides of the invention can be used in a variety of pharmaceutical, agricultural and industrial contexts. X═NO2, Cl, Br, NH2, OH, H, alkyl at one or several o, m, and p positions R═H or alkyl.
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(2012/07/27)

The design, synthesis and in vitro immunosuppressive evaluation of novel isobenzofuran derivatives
The synthesis and biological evaluation of a series of novel isobenzofuran-based compounds are described. The compounds were evaluated for their immunosuppressive effects of T-cell proliferation and IMPDH type II inhibitor activity in vitro, as well as their structure-activity relationships were assessed. Several compounds demonstrated highly efficacious immunosuppressive properties, especially compounds 2d, 2e, 2h and 2j, which were superior to MPA, while compounds 2k, 2m, 2n, 4c and 5d exhibited an equipotent inhibitory activity compared to MPA. Generally, it was obviously demonstrated that α,β-unsaturated amides proved more potent than the diamide and urea series. The present study provides a guide for further research on development of safe and effective immunosuppressive agents.
Yang, Na,Wang, Qing-He,Wang, Wen-Qian,Wang, Jian,Li, Feng,Tan, Shen-Peng,Cheng, Mao-Sheng
body text
p. 53 - 56
(2012/02/16)

β-alanine-DBU: A highly efficient catalytic system for knoevenagel-doebner reaction under mild conditions
A mild and efficient Knoevenagel-Doebner reaction from malonic acid and a wide range of aldehydes was catalyzed by a catalytic system consisting of β-alanine and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), affording the corresponding (E)-α,β-unsaturated carboxylic acids in good to excellent yields and with high stereoselectivity. The advantage of the method is that the reaction could proceed smoothly at ambient temperature so that it can tolerate a variety of functional groups and avoid unnecessary side reactions. Copyright
Zhu, Lingjian,Lei, Ning,Miao, Zhenyuan,Sheng, Chunquan,Zhuang, Chunlin,Yao, Jianzhong,Zhang, Wannian
experimental part
p. 139 - 143
(2012/03/09)

Lyase Enzymes, Nucleic Acids Encoding Them and Methods for Making and Using Them
This invention provides polypeptides having lyase activity, polynucleotides encoding these polypeptides, and methods of making and using these polynucleotides and polypeptides. In one aspect, the invention is directed to polypeptides having ammonia lyase activity, e.g., phenylalanine ammonia lyase, tyrosine ammonia lyase and/or histidine ammonia lyase activity, including thermostable and thermotolerant activity, and polynucleotides encoding these enzymes, and making and using these polynucleotides and polypeptides. The polypeptides of the invention can be used in a variety of pharmaceutical, agricultural and industrial contexts.
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(2011/02/25)

Manganese(III)-mediated phosphinoyl radical reactions for stereoselective synthesis of phosphinoylated tetrahydronaphthalenes
Reactions of diphenylphosphinoyl radicals with 5-aryl-2-pentenoates or β-phenylethylene styrenes generate trans-substituted tetrahydronaphthalenes through a cascade reaction sequence.
Pan, Xiang-Qiang,Wang, Lu,Zou, Jian-Ping,Zhang, Wei
supporting information; scheme or table
p. 7875 - 7877
(2011/09/12)

Synthesis, molecular modeling and biological evaluation of β-ketoacyl-acyl carrier protein synthase III (FabH) as novel antibacterial agents
A series of novel cinnamic acid secnidazole ester derivatives have been designed and synthesized, and their biological activities were also evaluated as potential inhibitors of FabH. These compounds were assayed for antibacterial activity against Escherichia coli, Pseudomonas aeruginosa, Bacillus subtilis and Staphylococcus aureus. Compounds with potent antibacterial activities were tested for their E. coli FabH inhibitory activity. Compound 3n showed the most potent antibacterial activity with MIC of 1.56-6.25 μg/mL against the tested bacterial strains and exhibited the most potent E. coli FabH inhibitory activity with IC50 of 2.5 μM. Docking simulation was performed to position compound 3n into the E. coli FabH active site to determine the probable binding conformation.
Zhang, Hong-Jia,Zhu, Di-Di,Li, Zi-Lin,Sun, Juan,Zhu, Hai-Liang
experimental part
p. 4513 - 4519
(2011/09/12)

Synthesis and anticancer activity of 13-membered cyclic enediynes
We herein describe the synthesis of 15 novel 13-membered cyclic enediyne derivatives using simple and straightforward approach. Representative examples were screened for their anticancer activities on 60 different human tumor cell lines representing various histologies viz. leukemia, melanoma, and cancers of lung, colon, kidney, ovary, breast, prostate, and central nervous system. The enediyne derivatives with halogen substitutions, especially fluorides were found to be active against most of the cell lines. The initial results indicates marginal to good inhibition for the growth of tumor cells for several cell lines, which shows the potential of these class of compound towards anticancer application. 15 novel 13-membered cyclic enediyne derivatives using a simple and straightforward approach are synthesized. The initial results show the potential of this class of compounds towards anticancer application. Copyright
Sharma, Mukul,Joshi, Mukesh C,Kumar, Vineet,Malhotra, Sanjay V.,Rawat, Diwan S.
scheme or table
p. 567 - 571
(2012/06/30)

Synthesis of cinnamic acid derivatives in a water-insoluble ionic liquid
A number of cinnamic acid derivatives have been synthesised from commercially available aromatic aldehydes and propanedioic acid in a water-insoluble ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate, [bmim]PF6) in high yields in the presence of small catalytic amounts of piperidine. The ionic liquid can be reused at least five times.
Zhang, Wensheng,Xu, Wenjing,Liu, Mei,Yan, Yuerong,Sun, Yuezhi,Zhang, Sheli
experimental part
p. 723 - 725
(2012/03/09)

NOVEL ACYL GUANIDINE DERIVATIVES
The present invention provides a pharmaceutical which possesses an excellent inhibitory effect on NHE3 (Na+/H+ exchanger type 3) and effectively improves diseases or conditions of organs in which NHE3 is expressed.
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Page/Page column 21

(2011/04/24)

The combination of 4-anilinoquinazoline and cinnamic acid: A novel mode of binding to the epidermal growth factor receptor tyrosine kinase
A novel type of cinnamic acid quinazoline amide derivatives (20-42), which designed the combination between quinazoline as the backbone and various substituted cinnamic acid as the side chain, have been synthesized and their biological activities were evaluated within cytotoxicity assay firstly and then potent EGFR inhibitory activity. Compound 42 demonstrated the most potent inhibitory activity (IC50 = 0.94 μM for EGFR), which could be optimized as a potential EGFR inhibitor in the further study. Docking simulation was performed to position compound 42 into the EGFR active site to determine the probable binding model. Analysis of the binding conformation of 42 in active site displayed compound 42 was stabilized by hydrogen bonding interactions with Lys822, which was different from other derivatives. In the further study, Compounds 43 and 44 had been synthesized and their biological activities were also evaluated, which were the same as that we expected. Compound 43 has demonstrated significant EGFR (IC50 = 0.12 μM) and tumor growth inhibitory activity as a potential anticancer agent.
Li, Dong-Dong,Lv, Peng-Cheng,Zhang, Hui,Zhang, Hong-Jia,Hou, Ya-Ping,Liu, Kai,Ye, Yong-Hao,Zhu, Hai-Liang
experimental part
p. 5012 - 5022
(2011/10/04)

Unravelling the olefin cross metathesis on solid support. Factors affecting the reaction outcome
Olefin cross metathesis on solid support under a variety of conditions is described. A comprehensive analysis considering diverse factors governing the reaction outcome gives a series of patterns for the application of this useful methodology in organic synthesis. If the intrasite reaction is not possible, homodimerization of the soluble olefin is crucial. When the homodimer is less reactive than its monomer, reaction outcome depends on the homodimerization rate, which, in turn, depends on the precatalyst used and the reaction conditions. If the site-site interaction is a feasible process, the cross metathesis product is obtained exclusively when the newly-formed double bond is resilient to further metathetic events. Taking into account these considerations, we have demonstrated that excellent results in terms of cross metathesis coupling can be obtained under the optimized conditions, and that microwave irradiation is also an interesting alternative for the development of a practical and energy-efficient cross metathesis on solid support.
Poeylaut-Palena, Andres A.,Mata, Ernesto G.
experimental part
p. 3947 - 3956
(2010/09/17)

Synthesis, molecular modeling, and biological evaluation of cinnamic acid metronidazole ester derivatives as novel anticancer agents
A series of novel cinnamic acid metronidazole ester derivatives have been designed and synthesized, and their biological activities were also evaluated as potential EGFR and HER-2 kinase inhibitors. Compound 3h showed the most potent biological activity (IC50 = 0.62 μM for EGFR and IC50 = 2.15 μM for HER-2). Docking simulation was performed to position compound 3h into the EGFR active site to determine the probable binding model. Antiproliferative assay results demonstrated that some of these compounds possessed good antiproliferative activity against MCF-7. Compound 3h with potent inhibitory activity in tumor growth inhibition may be a potential anticancer agent.
Qian, Yong,Zhang, Hong-Jia,Zhang, Hao,Xu, Chen,Zhao, Jing,Zhu, Hai-Liang
experimental part
p. 4991 - 4996
(2010/09/05)

Design and synthesis of novel 2-phenylaminopyrimidine (PAP) derivatives and their antiproliferative effects in human chronic myeloid leukemia cells
A series of novel 2-phenylaminopyrimidine (PAP) derivatives structurally related to STI-571 were designed and synthesized. The abilities of these compounds to inhibit proliferation were tested in human chronic myeloid leukemia K562 cells. (E)-3-(2-bromophenyl)-N-[4-methyl-3-(4-pyridin-3-yl-pyrimidin-2- ylamino)phenyl]acrylamide( 12d) was the most effective cell growth inhibitor and was 3-fold more potent than STI-571.
Chang, Sheng,Yin, Shi-Liang,Wang, Jian,Jing, Yong-Kui,Dong, Jin-Hua
experimental part
p. 4166 - 4179
(2009/12/28)

Phenylalanine aminomutase-catalyzed addition of ammonia to substituted cinnamic acids: A route to enantiopure α- and β-amino acids
(Chemical Equation Presented) An approach is described for the synthesis of aromatic α- and β-amino acids that uses phenylalanine aminomutase to catalyze a highly enantioselective addition of ammonia to substituted cinnamic acids. The reaction has a broad scope and yields substituted α- and β-phenylalanines with excellent enantiomeric excess. The regioselectivity of the conversion is determined by substituents present at the aromatic ring. A box model for the enzyme active site is proposed, derived from the influence of the hydrophobicity of substituents on the enzyme affinity toward various substrates.
Szymanski, Wiktor,Wu, Bian,Weiner, Barbara,De Wildeman, Stefaan,Feringa, Ben L.,Janssen, Dick B.
supporting information; experimental part
p. 9152 - 9157
(2010/03/01)

Solid-supported cross metathesis and the role of the homodimerization of the non-immobilized olefin
(Chemical Equation Presented) We have prepared immobilized olefins as models for the cross metathesis using different olefin partners in the presence of second generation Grubbs and Hoveyda-Grubbs precatalysts. We have demonstrated that solid-phase cross metathesis is strongly dependent on the degree of homodimerization of the non-immobilized olefin and the reactivity of such a homodimer. As in the homogeneous phase, the Hoveyda-Grubbs precatalyst was better for immobilized α,β-unsaturated carbonyl compounds.
Poeylaut-Palena, Andres A.,Testero, Sebastian A.,Mata, Ernesto G.
p. 2024 - 2027
(2008/09/19)

Development of efficient and reusable diarylphosphinopolystyrene-supported palladium catalysts for C-C bond forming cross-coupling reactions
Short and versatile syntheses of reusable diarylphosphinopolystyrene- supported palladium catalysts 3a-j are described. The bis(o-tolyl)phosphino catalyst 3b is particularly efficient for the Suzuki and Sonogashira cross-couplings, whereas the bis(m-tolyl)phosphino catalyst 3c is the most active catalyst for Heck reactions. The couplings are performed under non-anhydrous reaction conditions and require only low amounts of supported palladium (0.5 mequivs. for Suzuki-Miyaura, 1.0 mequiv. for Sonogashira and 0.5 mequivs. for Heck reactions could be sufficient). Catalysts 3a-j are recovered by filtration and can be reused more than four times with no loss of efficiency.
Schweizer, Stephane,Becht, Jean-Michel,Le Drian, Claude
p. 1150 - 1158
(2008/03/28)

Synthesis of trans-cinnamic acids from aryl aldehydes and aryl aldehyde bisulfite adducts with malonic acid using piperazine
Piperazine as a new reagent for the condensation of aryl aldehydes and their bisulfite adducts with malonic acid are described which afford the corresponding cinnamic acids in excellent yields and short reaction times in the absence of solvents under microwave irradiation.
Khosropour, Ahmad Reza,Khodaei, Mohammad Mehdi,Moghanian, Hassan
p. 364 - 365
(2007/10/03)

5-Nitrofuran-2-ylmethyl group as a potential bioreductively activated pro-drug system
5-Substituted isoquinolin-1-ones have been synthesised by one-pot Curtius rearrangement of the corresponding substituted 3-phenylpropenoyl azides and cyclisation. Arylmethylation of the anions of the isoquinolinones with benzyl halides [4-methoxybenzyl chloride, 2-(chloromethyl)furan and 5-nitro-2-(tosyloxymethyl)furan] takes place exclusively at nitrogen. Nitration of 2-(furan-2-ylmethyl)isoquinolin-1-one in strongly acidic medium gives 2-(5-nitrofuran-2-ylmethyl)isoquinolin-1-one, whereas weaker acidic conditions lead to dinitration. Curtius rearrangement of 3-carboranylbutanoyl azide and trapping with 5-nitrofuran-2-ylmethanol gives 5-nitrofuran-2-ylmethyl N-(3-carboranylpropyl)carbamate. Biomimetic reduction of these nitrofuranylmethyl derivatives of anticancer drugs triggers release of the parent drugs. Thus, these nitrofurans have potential applications as pro-drugs for selective release of therapeutic drugs in hypoxic solid tumours.
Berry, Jane M.,Watson, Corrine Y.,Whish, William J. D.,Threadgill, Michael D.
p. 1147 - 1156
(2007/10/03)

Iodide-promoted Debromination of Vicinal Dibromides. Part-I. In DMF
The specific rate constants and the activation parameters ΔH*, ΔS* and ΔG*, for the iodide-induced debromination reaction of erythro-2,3-dibromo-3-phenylpropanoic acids (o-Cl, -F, -Br, -NO2, -CH3; m-OCH3, -F, -NO2, -CH3 and p-NO2, -F, -Cl, -CH3) and erythro-2,3-dibromobutanoic acid in dimethylformamide are reported.Ortho-substituted compounds were found to react faster than the unsubstituted ones irrespective of the nature of the substituent.Results indicate that the bromine attached to the α-carbon atom is attacked by I- and the transition state is between non-synchronous nearly E1 type and synchronous E2 type.
Philip, V. J.,Mathai, I.M.,Raj, D. Joshwa Anthony,Jacob, G. Carol
p. 350 - 353
(2007/10/02)

Phosphite-Mediated in Situ Carboxyvinylation: A New General Acrylic Acid Synthesis
Sequential treatment of a 2-halo carboxylic acid with a dialkyl phosphite and an aldehyde or ketone in the presence of 3 equiv of sodium hydride in glyme constitutes a new general acrylic acid synthesis superior to conventional methods.An alkoxide-in-alcohol variant may be used with bromo- or chloroacetic acid and aryl aldehydes to produce cinnamic acids conveniently.The scope and other features of the synthesis are discussed.
Brittelli, David R.
p. 2514 - 2520
(2007/10/02)