- Synthesis and biological evaluation of thiophene [3,2-b] pyrrole derivatives as potential anti-inflammatory agents
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A series of thiophene [3,2-b] pyrrole derivatives were synthesized and evaluated their abilities to inhibit anti-inflammatory activity. In this series, substituent effects at the N-1, 2 and 5 positions of thiophene [3,2-b] pyrrole were examined. The results obtained are compared to those previously reported anti-inflammatory drugs like Tenidap sodium, Diclofenac sodium and Piroxicam. The results indicated the critical role of the group linked in the N-1 position and 2, 5 positions of thiophene [3,2-b] pyrrole with different functional groups.
- Rajender Kumar,Raju,Satish Goud,Sailaja,Sarma,Om Reddy,Prem Kumar,Krishna Reddy,Suresh,Hegde, Pragathi
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- Tunable spectroscopic and electrochemical properties of conjugated push-push, push-pull and pull-pull thiopheno azomethines
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Novel azomethines consisting uniquely of thiophene units were examined. The highly conjugated compounds were prepared by condensing air stable aminothiophenes with 2-thiophene aldehydes, which were substituted with various electronic groups. The resulting azomethines are highly conjugated and are both reductively and hydrolytically resistant. Various electron donating and accepting groups placed in the 2-position of 5-thiophene carboxaldehyde lead to electronically delocalized push-push, pull-pull, and push-pull azomethines. These electronic groups affect both the HOMO and the LUMO levels, which influence the absorption and emission spectra. Colors spanning the entire visible spectrum ranging from yellow to blue are possible with these nitrogen containing conjugated compounds. Excited state deactivation of the singlet excited state occurs predominately by internal conversion while only a small amount of energy is dissipated by intersystem crossing to the triplet state and by fluorescence. The ensuing fluorescence and phosphorescence of the thiopheno azomethines are similar to those of their thiophene analogues currently used in functional devices, but with the advantage of a low triplet state and tunable HOMO-LUMO energy levels extending from 3.0 to 1.9 eV. Quasi-reversible electrochemical radical cation formation is possible while the oxidation potential is dependent on the nature of the electronic group appended to the thiophene. The crystallographic data of the electronic push-push system show the azomethine bonds are planar and linear and they adopt the E isomer. The Royal Society of Chemistry 2007.
- Dufresne, Stephane,Bourgeaux, Marie,Skene
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- Characteristic flavor formation of thermally processed N-(1-deoxy-α-D-ribulos-1-yl)-glycine: Decisive role of additional amino acids and promotional effect of glyoxal
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The role of amino acids and α-dicarbonyls in the flavor formation of Amadori rearrangement product (ARP) during thermal processing was investigated. Comparisons of the volatile compounds and their concentrations when N-(1-deoxy-α-D-ribulos-1-yl)-glycine r
- Zhan, Huan,Cui, Heping,Yu, Junhe,Hayat, Khizar,Wu, Xian,Zhang, Xiaoming,Ho, Chi-Tang
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- Photo-on-Demand Synthesis of Vilsmeier Reagents with Chloroform and Their Applications to One-Pot Organic Syntheses
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The Vilsmeier reagent (VR), first reported a century ago, is a versatile reagent in a variety of organic reactions. It is used extensively in formylation reactions. However, the synthesis of VR generally requires highly toxic and corrosive reagents such as POCl3, SOCl2, or COCl2. In this study, we found that VR is readily obtained from a CHCl3 solution containing N,N-dimethylformamide or N,N-dimethylacetamide upon photo-irradiation under O2 bubbling. The corresponding Vilsmeier reagents were obtained in high yields with the generation of gaseous HCl and CO2 as byproducts to allow their isolations as crystalline solid products amenable to analysis by X-ray crystallography. With the advantage of using CHCl3, which bifunctionally serves as a reactant and a solvent, this photo-on-demand VR synthesis is available for one-pot syntheses of aldehydes, acid chlorides, formates, ketones, esters, and amides.
- Liang, Fengying,Eda, Kazuo,Okazoe, Takashi,Wada, Akihiro,Mori, Nobuaki,Konishi, Katsuhiko,Tsuda, Akihiko
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p. 6504 - 6517
(2021/05/06)
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- Preparation method of 5-methylthiophene-2-carboxaldehyde
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The invention relates to a preparation method of 5-methylthiophene-2-carboxaldehyde. The method comprises the following steps: putting N, N-dimethylformamide into a container at about 10-15 DEG C, carrying out low-temperature treatment for 1-2 hours for later use, putting 2-methylthiophene into an environment with the pH value of 7-8.5 at normal temperature, performing treating for 1-4 hours for later use, and slowly dropwise adding the treated 2-methylthiophene into the container filled with N, N-dimethylformamide; performing heating to 45-60 DEG C, fully performing stirring, carrying out heat preservation reaction for 3-5 hours, and absorbing tail gas generated in the reaction process with sodium hydroxide. Briefly speaking, according to the technical scheme, an excellent optimization scheme is utilized, and the problems existing in preparation of 5-methylthiophene-2-carboxaldehyde are solved.
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Paragraph 0028-0041
(2021/03/31)
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- Rhenium-Catalyzed Reduction of Carboxylic Acids with Hydrosilanes
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Re2(CO)10 efficiently catalyzes the direct reduction of various carboxylic acids under mild conditions (rt, irradiation 350 or 395 nm). While aliphatic carboxylic acids were readily converted to the corresponding disilylacetals with low catalyst loading (0.5 mol %) in the presence of Et3SiH (2.2 equiv), aromatic analogues required more drastic conditions (Re2(CO)10 5 mol %, Ph2MeSiH 4.0 equiv) to afford the corresponding aldehydes after acid treatment.
- Wei, Duo,Buhaibeh, Ruqaya,Canac, Yves,Sortais, Jean-Baptiste
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supporting information
p. 7713 - 7716
(2019/10/10)
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- Palladium-catalyzed C-H formylation of electron-rich heteroarenes through radical dichloromethylation
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A novel palladium-catalyzed C-H formylation of electron-rich N-, O-, and S-containing heteroarenes has been developed. The key to success is that the commercially available BrCHCl2 was used as a stoichiometric carbonyl source. Mechanistic investigations indicated that different from the known Reimer-Tiemann reaction, this net C-H formylation proceeded through an electrophilc radical-type path.
- Bao, Yan,Wang, Jian-Yong,Zhang, Ya-Xuan,Li, Yan,Wang, Xi-Sheng
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supporting information
p. 3147 - 3150
(2018/07/13)
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- Reduction of N,N-Dimethylcarboxamides to Aldehydes by Sodium Hydride–Iodide Composite
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A new and concise protocol for selective reduction of N,N-dimethylamides into aldehydes was established using sodium hydride (NaH) in the presence of sodium iodide (NaI) under mild reaction conditions. The present protocol with the NaH-NaI composite allows for reduction of not only aromatic and heteroaromatic but also aliphatic N,N-dimethylamides with wide substituent compatibility. Retention of α-chirality in the reduction of α-enantioriched amides was accomplished. Use of sodium deuteride (NaD) offers a new step-economical alternative to prepare deuterated aldehydes with high deuterium incorporation rate. The NaH-NaI composite exhibits unique chemoselectivity for reduction of N,N-dimethylamides over ketones.
- Chan, Guo Hao,Ong, Derek Yiren,Yen, Zhihao,Chiba, Shunsuke
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- Systematic structure-activity relationship (SAR) exploration of diarylmethane backbone and discovery of a highly potent novel uric acid transporter 1 (URAT1) inhibitor
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In order to systematically explore and better understand the structure-activity relationship (SAR) of a diarylmethane backbone in the design of potent uric acid transporter 1 (URAT1) inhibitors, 33 compounds (1a-1x and 1ha-1hi) were designed and synthesized, and their in vitro URAT1 inhibitory activities (IC50) were determined. The three-round systematic SAR exploration led to the discovery of a highly potent novel URAT1 inhibitor, 1h, which was 200-and 8-fold more potent than parent lesinurad and benzbromarone, respectively (IC50 = 0.035 μM against human URAT1 for 1h vs. 7.18 μM and 0.28 μM for lesinurad and benzbromarone, respectively). Compound 1h is the most potent URAT1 inhibitor discovered in our laboratories so far and also comparable to the most potent ones currently under development in clinical trials. The present study demonstrates that the diarylmethane backbone represents a very promising molecular scaffold for the design of potent URAT1 inhibitors.
- Cai, Wenqing,Wu, Jingwei,Liu, Wei,Xie, Yafei,Liu, Yuqiang,Zhang, Shuo,Xu, Weiren,Tang, Lida,Wang, Jianwu,Zhao, Guilong
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- Palladium-catalyzed regioselective allylation of five-membered heteroarenes with allyltributylstannane
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Palladium-catalyzed allylation reactions of 2-(chloromethyl)thiophenes, 2-(chloromethyl)furans, and N-protected 2-(chloromethyl)-1H-pyrroles with allyltributylstannane were described in this study. This type of allylation reaction regioselectively occurred on the heteroarene rings to produce allylated dearomatization products or allylated heteroarenes with satisfactory yields.
- Zhang, Sheng,Yu, Xiaoqiang,Feng, Xiujuan,Yamamoto, Yoshinori,Bao, Ming
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supporting information
p. 3842 - 3845
(2015/03/30)
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- Candida parapsilosis ATCC 7330 mediated oxidation of aromatic (activated) primary alcohols to aldehydes
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A green, simple and high yielding [up to 86% yield] procedure is developed for the oxidation of aromatic (activated) primary alcohols to aldehydes using whole cells of Candida parapsilosis ATCC 7330. The biotransformation is carried out under mild conditions at 25 °C, in hexane: water (48 : 2) (v/v).
- Sivakumari, Thakkellapati,Chadha, Anju
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p. 91594 - 91600
(2015/11/10)
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- Electrochromic properties of novel chalcones containing triphenylamine moiety
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A series of novel electrochromic chalcones containing triphenylamine units were synthesized by Aldol reaction and characterized by NMR, IR and MS. Their optical, electrochemical properties were investigated using UV-vis, photoluminescence spectra and cyclic voltammetry. The molecular orbital energy levels and excitation energies were calculated by quantum chemical calculation. It was found that the fluorescence intensity is decreasing with formation of charge-transfer state. The existence of electron donating group on triphenylamine unites caused a significant bathochromic shift of the UV absorption maximum and increased EHOMO and ELUMO. The electrochromic property of the synthesized compounds was studied by spectroelectrochemical experiments. The results showed that the chalcones containing triphenylamine moiety presented good electrochromic stability, with a color change from yellow to blue as applied potentials ranging from 0.0 to 2.8 V. The coloring and bleaching time was in the range of 2.9-4.2 s and 1.7-3.3 s, respectively.
- Jin, Huiyi,Li, Xianggao,Tan, Tingfeng,Wang, Shirong,Xiao, Yin,Tian, Jianhua
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p. 154 - 160
(2014/04/17)
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- Synthesis of novel thiophene-based chiral ligands and their application in asymmetric Henry reaction
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Novel chiral thiolated amino alcohols were synthesized from norephedrine and thiophene carbaldehydes (methyl- or ethyl-substituted) and applied to the catalytic asymmetric Henry reaction of various aldehydes with nitromethane to provide β-hydroxy nitroalkanols in high conversion (92%). The reaction was optimized in terms of the metal, solvent, temperature and amount of chiral ligand. The corresponding catalyst with Cu(OTf)2 and 2-propanol as the solvent provided the best enantioselectivities (up to 96% ee) of the corresponding nitroalcohols for aliphatic aldehydes. Copyright 2013 John Wiley & Sons, Ltd. Chiral thiophene contanining amino alcohol ligands were synthesized from norephedrine and substituted 5-thiophene-2-carbaldehyde. This novel chiral ligands were used to catalyze enantioselective Henry reaction of various aldehydes and nitroalkanes in high yields with good to high enantio- and diastereoselectivities. Copyright
- Aydin, A. Ebru
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p. 283 - 289
(2013/06/27)
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- Generation of metalated thiophenes with Grignard reagent and catalytic secondary amine for the cross coupling reaction with aryl halides
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The reaction of thiophene derivatives with Grignard reagent (EtMgCl) and a catalytic amount of amine (Cy2NH) induced the metalation at the α-position. Following addition of several aryl halides in the presence of a nickel or palladium catalyst afforded C-H arylated products in good to excellent yields. The method was successfully applied to facile synthesis of differently-substituted 2,5-diarylthiophenes.
- Tanaka, Shota,Tanaka, Daiki,Sugie, Atsushi,Mori, Atsunori
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experimental part
p. 1173 - 1176
(2012/03/26)
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- Multi-alkylthienyl appended porphyrins for efficient dye-sensitized solar cells
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Four porphyrin dyes, incorporating multi-alkylthienyl appended porphyrins as the electron donor, the 2-cyanoacrylic acid as the electron acceptor, and different π-conjugated spacer, have been synthesized for dye-sensitized solar cells (DSSCs). All the porphyrin dyes studied in this work exhibit red-shifted and broadened electronic spectra respect to the reference PZn as expected. By the introduction of thienyl groups at the meso-positions, the energy level of Eox (excited-state oxidation potentials) is significantly shifted to the positive compared with the reference P Zn, indicating a decreased HOMO-LUMO gap. The highest power conversion efficiency of the four dyes based on DSSCs reached 5.71% under AM 1.5 G irradiation.
- Zhou, Weiping,Zhao, Bin,Shen, Ping,Jiang, Shenghui,Huang, Hongduan,Deng, Lijun,Tan, Songting
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scheme or table
p. 404 - 412
(2012/07/01)
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- Modulating reactivity and diverting selectivity in palladium-catalyzed heteroaromatic direct arylation through the use of a chloride activating/blocking group
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(Chemical Equation Presented) Through the introduction of an aryl chloride substituent, the selectivity of palladium-catalyzed direct arylation may be diverted to provide alternative regioisomeric products in high yields. In cases where low reactivity is typically observed, the presence of the carbon-chlorine bond can serve to enhance reactivity and provide superior outcomes. From a strategic perspective, the C-Cl bond is easily introduced and can be employed in a variety of subsequent transformations to provide a wealth of highly functionalized heterocycles with minimal substrate preactivation. The impact of the C-Cl functional group on direct arylation reactivity has also been evaluated mechanistically, and the observed reactivity profiles correlate very well with that predicted by a concerted metalation-deprotonation pathway.
- Liegault, Benoit,Petrov, Ivan,Gorelsky, Serge I.,Fagnou, Keith
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supporting information; experimental part
p. 1047 - 1060
(2010/04/04)
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- Evaluation of electron-deficient phosphine ligands for direct arylation of heterocycles
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New electron-deficient biarylphosphine ligands were studied and proved to be efficient for the direct arylation of heteroarenes with aryl iodides. The ability of a more electron-deficient palladium centre to accelerate the arylation of heterocycles that remained unreactive with aryl iodides in the past has been validated and these heteroarenes can now be smoothly reacted in the presence of a new electrophilic catalyst. Experimental evidence suggests a viable concerted metalation-deprotonation pathway for the C-H bond cleavage step with an electron-deficient palladium centre.
- Rene, Olivier,Fagnou, Keith
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scheme or table
p. 2116 - 2120
(2010/11/04)
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- PROCESS FOR PRODUCING AROMATIC NITRILE COMPOUND
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A novel process for industrially producing an aromatic nitrile compound represented by the following general formula (3):characterized in that one of an aromatic hydroxymethyl compound, an aromatic alkoxymethyl compound and an aromatic aldehyde compound, all represented by the following general formula (1): or a mixture thereof is reacted with an oxidized bromine compound represented by the general formula (2)MBrOm in the presence of an acid catalyst and either ammonia or an ammonium sat.
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Page/Page column 25-26
(2008/06/13)
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- Isoquinoline compound melanocortin receptor ligands and methods of using same
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The invention relates to melanocortin receptor ligands and methods of using the ligands to alter or regulate the activity of a melanocortin receptor. The invention further relates to tetrahydroisoquinoline aromatic amines that function as melanocortin receptor ligands and as agents for controlling cytokine-regulated physiologic processes and pathologies, and combinatorial libraries thereof.
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- Process for production of 2-thiophene aldehydes
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There is disclosed a process for the production of 2-thiophene aldehydes, in which the 2-thiophene aldehydes are obtained by the formylation of thiophene or derivatives thereof with formamides and phosgene.
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- Anodic Methoxylation of 2,5-Dimethyl- and Tetramethyl-thiophene. Formation and Transformation of 2,5-Dimethoxy Adducts
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The electrooxidation of 2,5-dimethyl- and tetramethyl-thiophene in methanol containing sodium methoxide produced isomeric mixtures (in either case 40percent cis, 60percent trans) of the corresponding 2,5-dimethoxy adducts each in 30percent yield, together with side-chain oxidation products.During GLC analysis a portion of the 2,5-dimethoxy adduct of 2,5-dimethylthiophene loses a methanol molecule to give 2,5-dihydro-2-methoxy-2-methyl-5-methylenethiophene.By contrast, the 2,5-dimethoxy adduct of the tetramethyl compound remained intact to GLC.In CDCl3 solution in an NMR tube, each isomer of the 2,5-dimethoxy adducts was transformed into the corresponding 2-(methoxymethyl)thiophene.When sodium acetate was used as electrolyte, the products were the corresponding 2-(methoxymethyl)thiophenes plus thiophene-2-carbaldehydes.In order to synthesize 2-acetoxymethyl-5-methylthiophene as a reference compound, anodic acetoxylation of 2,5-dimethylthiophene was also examined.
- Yoshida, Kunihisa,Takeda, Kazusada,Fueno, Takayuki
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p. 2817 - 2820
(2007/10/02)
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- Lithiation of Heterocycles Directed by α-Amino Alkoxides
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The addition of heterocyclic aromatic aldehydes to certain lithium dialkylamides gave α-amino alkoxides that were ring-lithiated with butyllithium.Alkylation and hydrolysis provided ring-substituted heterocyclic aromatic aldehydes via a one-pot reaction.The metalation of α-amino alkoxides derived from thiophenecarboxaldehydes, furaldehydes, N-methylpyrrolecarboxaldehydes, and indolecarboxaldehydes was examined.The regioselectivity of the lithiation, was dependent on the heterocycle, the amine component of the α-amino alkoxide, and the metalation conditions.A novel N-methyl metalation of α-amino alkoxides derived from N-methylpyrrole-2-carboxaldehyde and N-methylindole-2-carboxaldehyde was achieved when N,N,N'-trimethylethylenediamine was used as the amine component for in situ formation of the α-amino alkoxides.The novel directed N-methyl lithiations are attributed to an intramolecular TMEDA-like assisted metalation.
- Comins, Daniel L.,Killpack, Michael O.
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p. 104 - 109
(2007/10/02)
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- CHEMOSELECTIVE PROTECTION OF HETEROAROMATIC ALDEHYDES AS IMIDAZOLIDINE DERIVATIVES. PREPARATION OF 5-SUBSTITUTED FURAN- AND TIOPHENE-2-CARBOXALDEHYDES VIA METALLO-IMIDAZOLIDINE INTERMEDIATES
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Furan-, tiophene- and N-methylpyrrole-2-carboxaldehydes may be transformed into the corresponding N,N'-dimethylimidazolidines in a reaction not requiring acid catalysis.The resulting furan and tiophene (but not N-methylpyrrole) derivatives may be metallated in high yields and the carboxaldehyde functionality regenerated under very mild conditions.Treatment of the aldehydoketone 2-acetyl-5-formylthiophene with N,N'-dimethylethylenediamine gives only the product of reaction at the aldehyde function thus establishing this methodology as a potentially valuable method for the protection of an aldehyde in the presence of a ketone.
- Carpenter, Andrew J,,Chadwick, Derek J.
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p. 3803 - 3812
(2007/10/02)
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