- Mild Darzens Annulations for the Assembly of Trifluoromethylthiolated (SCF3) Aziridine and Cyclopropane Structures
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We report mild new annulation approaches to trisubstituted trifluoromethylthiolated (SCF3) aziridines and cyclopropanes via Darzens inspired protocols. The products of these anionic annulations, rarely studied previously, possess attractive features rendering them valuable building blocks for synthesis platforms. In this study, trisubstituted acetophenone nucleophiles bearing SCF3 and bromine substituents in their α position were shown to undergo [2 + 1] annulations with vinyl ketones and tosyl-protected imines under mild reaction conditions.
- Delost, Michael D.,Njardarson, Jon T.
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p. 6121 - 6125
(2021/08/16)
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- Magnesium Halide-Catalyzed Synthesis of Oxaspiro[2.5]octenes from a Methylenecyclopropane and Acyl Cyanoalkenes
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MgX2-catalyzed annulation of methylenecyclopropanes with acyl cyanoalkenes was accomplished to give oxaspiro[2.5]octenes in excellent yields. The reaction proceeded through a rare intramolecular oxa-Michael addition of Mg enolate. The oxaspiro
- Ogura, Kazuki,Shibata, Ikuya,Shimazu, Jun-ya,Suzuki, Itaru
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supporting information
p. 2785 - 2787
(2021/06/26)
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- Substituent-Controlled Divergent Cascade Cycloaddition Reactions of Chalcones and Arylalkynols: Access to Spiroketals and Oxa-Bridged Fused Heterocycles
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Herein, we report substituent-controlled divergent cascade cycloaddition reactions of chalcones and arylalkynols in the presence of PtI2. Depending on the substituent on the chalcone, either spiroketals or oxa-bridged fused heterocycles could be obtained in the ranges of 86–97% and 87–95% yields under identical reaction conditions. Control experiments were carried out to elucidate the origin of the high chemoselectivity. These provide a method for the synthesis of a diverse array of structurally complex oxygen-containing heterocycles. (Figure presented.).
- Chang, Weixing,Kong, Jingyang,Li, Jing,Liu, Lingyan,Wang, Hongkai,Zeng, Tianlong
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supporting information
p. 4024 - 4032
(2021/07/12)
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- Development of Tyrphostin Analogues to Study Inhibition of the Mycobacterium tuberculosis Pup Proteasome System**
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Tuberculosis is a global health problem caused by infection with the Mycobacterium tuberculosis (Mtb) bacteria. Although antibiotic treatment has dramatically reduced the impact of tuberculosis on the population, the existence and spreading of drug resist
- Janssen, Guido V.,Zhang, Susan,Merkx, Remco,Schiesswohl, Christa,Chatterjee, Champak,Darwin, K. Heran,Geurink, Paul P.,van der Heden van Noort, Gerbrand J.,Ovaa, Huib
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p. 3082 - 3089
(2021/09/14)
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- HETEROCYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE INCLUDING SAME
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The present specification relates to a hetero-cyclic compound and an organic light emitting device comprising the same.
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Paragraph 0142; 0143
(2018/03/10)
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- Dienamine-Mediated Asymmetric Inverse-Electron-Demand Hetero-Diels–Alder Reaction of Linear Deconjugated Enones: Diversity-Oriented Synthesis of 3,4-Dihydropyrans
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The first organocatalytic asymmetric inverse-electron-demand Diels–Alder reaction of deconjugated enones by using a linear dienamine was explored. Electron-poor oxadienes having a cyano group were found to be suitable in this reaction. With a 20 mol-% loa
- Maity, Rajendra,Pan, Subhas Chandra
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supporting information
p. 871 - 874
(2017/02/15)
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- Organocatalytic Asymmetric [4+2] Cycloaddition of 1-Acetylcyclopentene and 1-Acetylcyclohexene for the Synthesis of Fused Carbocycles
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The first organocatalytic asymmetric [4+2]-cycloaddition reaction of 1-acetylcyclopentenes and 1-acetylcyclohexenes was developed. Enones having cyano groups were used as the dienophiles in this method. The reaction provides a useful practical route to th
- Nath, Utpal,Pan, Subhas Chandra
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supporting information
p. 6457 - 6461
(2017/12/01)
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- Development of 1H-Pyrazolo[3,4-b]pyridines as Metabotropic Glutamate Receptor 5 Positive Allosteric Modulators
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The metabotropic glutamate receptor 5 (mGluR5) is an attractive target for the treatment of schizophrenia due to its role in regulating glutamatergic signaling in association with the N-methyl-d-aspartate receptor (NMDAR). We describe the synthesis of 1H-pyrazolo[3,4-b]pyridines and their utility as mGluR5 positive allosteric modulators (PAMs) without inherent agonist activity. A facile and convergent synthetic route provided access to a structurally diverse set of analogues that contain neither the aryl-acetylene-aryl nor aryl-methyleneoxy-aryl elements, the predominant structural motifs described in the literature. Binding studies suggest that members of our new chemotype do not engage the receptor at the MPEP and CPPHA mGluR5 allosteric sites. SAR studies culminated in the first non-MPEP site PAM, 1H-pyrazolo[3,4-b]pyridine 31 (BMT-145027), to improve cognition in a preclinical rodent model of learning and memory.
- Hill, Matthew D.,Fang, Haiquan,Brown, Jeffrey M.,Molski, Thaddeus,Easton, Amy,Han, Xiaojun,Miller, Regina,Hill-Drzewi, Melissa,Gallagher, Lizbeth,Matchett, Michele,Gulianello, Michael,Balakrishnan, Anand,Bertekap, Robert L.,Santone, Kenneth S.,Whiterock, Valerie J.,Zhuo, Xiaoliang,Bronson, Joanne J.,Macor, John E.,Degnan, Andrew P.
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supporting information
p. 1082 - 1086
(2016/12/18)
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- One-pot highly diastereoselective annulation to N-unprotected tetrasubstituted 2-pyrrolines
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A one-pot DABCO-catalysed Michael addition of glycine imine-derived esters to trans-2-aroyl-3-arylacrylonitriles followed by a deprotection/cyclization/tautomerization sequence afforded tetrasubstituted N-unprotected trans-2-pyrrolines in up to 96% yield.
- Meninno, Sara,Capobianco, Amedeo,Peluso, Andrea,Lattanzi, Alessandra
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supporting information
p. 2137 - 2140
(2015/04/27)
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- IBX-mediated dehydrogenation of substituted β-oxonitriles
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A convenient method for the mild dehydrogenation of β-oxonitriles is presented. When treated with o-iodoxybenzoic acid (IBX), a range of these compounds were transformed into their unsaturated counterparts. Furthermore, we show that the products of the dehydrogenation can react in situ, undergoing rapid hetero-Diels-Alder reactions with enol ethers to give multiply substituted dihydropyrans. We also describe the dehydrogenation of cyclic β-oxonitriles, which leads to the formation of substituted phenols. Copyright
- Klahn, Philipp,Kirsch, Stefan F.
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p. 3149 - 3155
(2014/06/09)
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- Reduced graphene oxide supported piperazine in aminocatalysis
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Reduced graphene oxide (rGO) has been used as a support for piperazine to provide a heterogeneous bifunctional organocatalyst (rGO-NH) that is able to efficiently promote vintage organic transformations such as Knoevenagel, Michael and aldol reactions. The obtained results suggest a significant role of the support in the course of these reactions. This journal is the Partner Organisations 2014.
- Rodrigo, Eduardo,García Alcubilla, Beatriz,Sainz, Raquel,Fierro, J. L. García,Ferritto, Rafael,Cid, M. Belén
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supporting information
p. 6270 - 6273
(2014/06/09)
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- Asymmetric synthesis of trisubstituted tetrahydrothiophenes bearing a quaternary stereocenter via double michael reaction involving dynamic kinetic resolution
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The stereoselective synthesis of highly functionalized tetrahydrothiophenes bearing three contiguous stereocenters, one of them quaternary, can be achieved by reacting trans-α-cyano-α,β-unsaturated ketones and trans-tert-butyl 4-mercapto-2-butenoate in the presence of a readily available amine thiourea. The products are obtained in high yield, good diastereoselectivity, and excellent enantioselectivity. The overall formation of tetrahydrothiophenes occurs via a cascade double Michael reaction involving a highly efficient process of dynamic kinetic resolution.
- Meninno, Sara,Croce, Gianluca,Lattanzi, Alessandra
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supporting information
p. 3436 - 3439
(2013/07/26)
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- Microwave synthesis of α-cyano chalcones
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A novel methodology for facile production of α-cyano chalcones under microwave irradiation is described. Utilizing a Knoevenagel condensation between benzoylacetonitriles and aromatic aldehydes, substituted chalcones are generated via a 15-min, one-pot synthesis. Diversification of aromatic groups, including electron-withdrawing, electron-donating, and heterocyclic substitutions, has led to the isolation of over twenty colored, solid chalcone products. Furthermore the methodology can be extended to the synthesis of benzylidenemalononitriles as well as methyl and ethyl α-cyano cinnamates.
- Deshpande, Shyam J.,Leger, Paul R.,Sieck, Stephen R.
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supporting information; experimental part
p. 1772 - 1775
(2012/05/04)
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- Fe-catalyzed allylic C-C-bond activation: Vinylcyclopropanes as versatile a1,a3,d5-synthons in traceless allylic substitutions and [3 + 2]-cycloadditions
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The low-valent iron complex Bu4N[Fe(CO)3(NO)] (TBAFe) catalyzes the allylic C-C-bond activation of electron-poor vinyl cyclopropanes to generate synthetically useful a1,a3,d5-synthons which are prone to undergo multiple consecutive reactions. The versatility of this approach is demonstrated by a traceless allylic substitution and a formal [3 + 2] cycloaddition to give either functionalized acyclic products or densely substituted cyclopentanes and pyrrolidines in high yields and regioselectivities.
- Dieskau, Andre P.,Holzwarth, Michael S.,Plietker, Bernd
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supporting information; experimental part
p. 5048 - 5051
(2012/05/05)
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- Tandem cross-Rauhut-Currier/cyclization reactions of activated alkenes to give densely functionalized 3,4-dihydropyrans
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A novel tandem cross-Rauhut-Currier/cyclization reaction between α,β-unsaturated ketones was developed. Using DABCO (20 mol %) as the catalyst, a series of densely functionalized 3,4-dihydropyrans were obtained in excellent yields and stereoselectivities (up to 98% yield, >99:1 dr). A tentative catalytic cycle was proposed with key intermediates confirmed by ESIMS studies.
- Liu, Wen,Zhou, Jing,Zheng, Changwu,Chen, Xingkuan,Xiao, Hua,Yang, Yingquan,Guo, Yinlong,Zhao, Gang
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p. 1768 - 1773
(2011/04/15)
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- Enantioselective nitrocyclopropanation of α,β-unsaturated α-cyanoimides catalyzed by bifunctional thiourea
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The organocatalyzed asymmetric cyclopropanation of bromonitromethane with α-cyano-α,β-unsaturated imides is described. In addition, the same bifunctional thiourea was revealed to be a powerful catalyst for preparing these α-cyanoimides by Knoevenagel condensation. Georg Thieme Verlag Stuttgart.
- Inokuma, Tsubasa,Sakamoto, Shota,Takemoto, Yoshiji
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experimental part
p. 1627 - 1630
(2009/12/08)
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- Superacid-catalyzed intramolecular cyclization reaction of arylcyanopropionate: Geminal substitution effect on superelectrophilicity
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(Chemical Equation Presented) We present superacid-catalyzed intramolecular cyclization reactions of arylcyanopropionates to give cyclized five- and six-membered β-enamino esters in moderate to high yields. Known intramolecular ring-closing reactions of protonated nitrile to aromatic carbon atom are limited to the 6-membered case. Interestingly, a significant synergistic increase of reactivity of the cyano functionality was observed, and the cyano nitrogen atom was converted into an amino group, when an ester group was present in a geminal arrangement. Deuterium exchange experiments excluded the involvement of deprotonation of the α-proton in the cyclization process. The acidity dependence of the cyclization reactions and 13C NMR studies of a model compound, methyl cyanoacetate, in various acidic media were consistent with the involvement of the O,N-diprotonated dication of methyl cyanoacetate, a distonic dication, in strong acid, and this is considered to be the de facto electrophile in the present cyclization reaction of arylcyanopropionates.
- Nakamura, Satoshi,Sugimoto, Hiromichi,Ohwada, Tomohiko
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p. 4219 - 4224
(2008/09/20)
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- Efficient synthesis of 4-cyano 2,3-dihydrooxazoles by direct amination of 2-alkylidene 3-oxo nitriles
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The addition of N-protected O-sulfonyl hydroxylamine derivatives on 2-alkylidene 3-oxo nitrites gives 2,5-disubstituted 4-cyano 2,3-dihydrooxazoles (4-oxazolines) by a practical and efficient synthetic procedure under very mild conditions in high yields. Likely, the formation of N,O-heterocycles proceeds through a domino reaction involving a fast rearrangement of unstable 2-acyl 2-cyano aziridines. Georg Thieme Verlag Stuttgart.
- Burini, Edoardo,Fioravanti, Stefania,Morreale, Alberto,Pellacani, Lucio,Tardella, Paolo A.
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p. 2673 - 2675
(2007/10/03)
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- Preparation of α-functionalized alkenylmagnesium reagents via a halide-magnesium exchange
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A general preparation of alkenylmagnesium derivatives bearing an electron-withdrawing function in the α-position (Y=CN, CO2R, CONR2, SO2Ph) has been made possible by using a low temperature (-40 to -30°C) bromine-magnesium exchange with i-PrMgBr in THF. This reaction has also been used to prepare 5-magnesiated-1,3-dioxin-4-one derivatives bearing an alkoxy substituent in β-position to the carbon-magnesium bond.
- Thibonnet, Jér?me,Anh Vu, Viet,Bérillon, Laurent,Knochel, Paul
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p. 4787 - 4799
(2007/10/03)
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- Pyridine Syntheses. II. Condensation Routes Toward Streptonigrin Ring C [1]
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Alternative complimentary syntheses of penta-substituted pyridine rings with full regiochemical control of substituents were studied as a method for the synthesis of Streptonigrin (1). Various α-substituted acetophenones 2 were reacted with enones 3 in acetic acid/ammonium acetate and air to afford penta-substituted pyridines 4. α-Substituents that could provide a source of exocyclic nitrogen at position 3 of these Steptonigrin ring-C models proved to be the limiting factor. However, an inverse "3+2+1" cyclocondensation of α-cyanochalcone 5c with 2-furyl ethyl ketone (6b) afforded the desired model 6-(2-furyl)-5-methyl-2,4-diphenyl-3-pyridinecarbonitrile (4g) in 75% yield.
- Robinson, J. Michael,Ahmed, Masood,Alaniz, Nicky J.,Boyles, Timothy P.,Brasher, Chris D.,Floyd, Kimberly A.,Holland, Preston L.,Maruffo, Laura D.,McMahan, Terry L.,Middleton, Stan,O'Hara, Kevin D.,Pack, Marcia J.,Reynolds, Brandon D.,Rodriquez, Romelia R.,Sawyer, Dennis E.,Sharp, Elena,Simpson, Sharai L.,Vanlandingham, Clint L.,Velasquez, Rebecca S.,Welch, Brian M.,Wright, C. David
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- Hetero-Diels-Alder Reaction of 3-Aryl-2-benzoyl-2-propenenitriles with Enol Ethers. Synthesis of 2-Alkoxy-3,4-dihydro-2H-pyran-5-carbonitriles
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The hetero-Diels-Alder reaction of 3-aryl-2-benzoyl-2-propenenitriles 1a-d with enol ethers 2a-c yields cis/trans diastereoisomers of 2-alkoxy-4,6-diaryl-3,4-dihydro-2H-pyran-5-carbonitriles 3 and 4 in 79-98% yield. The similar reaction of 1a-c with cyclic enol ether 5 affords diastereoisomeric cycloadducts 6 and 7 with cis annulated pyran rings. Reaction of 3 with sulfuric acid leads to 2-hydroxy-3,4-dihydro-2H-pyran-5-carbonitriles 8 and 9.
- Bogdanowicz-Szwed,Palasz
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p. 1157 - 1172
(2007/10/03)
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- N-Benzylidenebenzenesulfonamide as a benzaldehyde equivalent in the Knoevenagel reaction
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N-Benzylidenebenzenesulfonamide was shown to be a useful benzaldehyde equivalent in the Knoevenagel Reaction for cyana-containing active methylene compounds. The intermediate β-N-benzenesulfonylamino carbonyl derivatives from other active methylene compounds failed to undergo elimination.
- Zajac Jr.,Walters,Buzby,Gagnon,Labroli
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p. 427 - 432
(2007/10/02)
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