- Rh2(II)-Catalyzed intermolecular N-Aryl aziridination of olefins using nonactivated N atom precursors
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The development of the first intermolecular Rh2(II)-catalyzed aziridination of olefins using anilines as nonactivated N atom precursors and an iodine(III) reagent as the stoichiometric oxidant is reported. This reaction requires the transfer of an N-aryl nitrene fragment from the iminoiodinane intermediate to a Rh2(II) carboxylate catalyst; in the absence of a catalyst only diaryldiazene formation was observed. This N-aryl aziridination is general and can be successfully realized by using as little as 1 equiv of the olefin. Di-, tri-, and tetrasubstituted cyclic or acylic olefins can be employed as substrates, and a range of aniline and heteroarylamine N atom precursors are tolerated. The Rh2(II)-catalyzed N atom transfer to the olefin is stereospecific as well as chemo- and diastereoselective to produce the N-aryl aziridine as the only amination product. Because the chemistry of nonactivated N-aryl aziridines is underexplored, the reactivity of N-aryl aziridines was explored toward a range of nucleophiles to stereoselectively access privileged 1,2-stereodiads unavailable from epoxides, and removal of the N-2,4-dinitrophenyl group was demonstrated to show that functionalized primary amines can be constructed.
- Deng, Tianning,Mazumdar, Wrickban,Yoshinaga, Yuki,Patel, Pooja B.,Malo, Dana,Malo, Tala,Wink, Donald J.,Driver, Tom G.
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supporting information
p. 19149 - 19159
(2021/11/23)
-
- Discovery of Hydroxyamidine Derivatives as Highly Potent, Selective Indoleamine-2,3-dioxygenase 1 Inhibitors
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In this study, a series of novel hydroxyamidine derivatives were identified as potent and selective IDO1 inhibitors by structure-based drug design. Among them, compounds 13-15 and 18 exhibited favorable enzymatic and cellular activities. Compound 18 showed improved bioavailability in mouse, rat, and dog (F% = 44%, 58.8%, 102.1%, respectively). With reasonable in vivo pharmacokinetic properties, compound 18 was further evaluated in a transgenic MC38 xenograft mouse model. The combination of compound 18 with PD-1 monoclonal antibody showed a synergistic antitumor effect. These data indicated that compound 18 as a potential cancer immunotherapy agent should warrant further investigation.
- Jin, Fangfang,Hu, Qiyue,Fei, Hongbo,Lv, Hejun,Wang, Shenglan,Gui, Bin,Zhang, Junzhen,Tu, Wangyang,Zhang, Yun,Zhang, Lei,Wan, Hong,Zhang, Limin,Hu, Bin,Yang, Fanglong,Bai, Chang,He, Feng,Zhang, Lianshan,Tao, Weikang
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supporting information
p. 195 - 201
(2021/02/06)
-
- Mechanistic investigation on the remote stereocontrol in the chiral Lewis base-catalyzed, SiCl4-promoted kinetic resolution of chlorinated cis-vinyl epoxides
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It has been known that the enantioselectivity of the chiral Lewis base-catalyzed, SiCl4-promoted kinetic resolution of α,β-dichloro cis-vinyl epoxide is highly influenced by the configuration of the distal β-chlorine-bearing stereocenter. In th
- Jung, Jungi,Song, Mugeon,Choi, Jun-Ho,Chung, Won-jin
-
-
- Straightforward Synthesis of Fluorinated Enals via Photocatalytic α-Perfluoroalkenylation of Aldehydes
-
(Per)fluorinated substances represent an important compound class with regard to drug design and material chemistry. We found a mild, operationally simple, and inexpensive photocatalytic perfluoroalkenylation reaction giving tetrasubstituted, highly electron-deficient enals straight from aldehydes. This one-step reaction tolerates various functional groups and can be applied to a wide range of substrates giving the products in yields of 52-84%.
- Wulkesch, Christian,Czekelius, Constantin
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p. 7425 - 7438
(2021/06/21)
-
- The formyloxyl radical: Electrophilicity, C-H bond activation and anti-Markovnikov selectivity in the oxidation of aliphatic alkenes
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In the past the formyloxyl radical, HC(O)O, had only been rarely experimentally observed, and those studies were theoretical-spectroscopic in the context of electronic structure. The absence of a convenient method for the preparation of the formyloxyl radical has precluded investigations into its reactivity towards organic substrates. Very recently, we discovered that HC(O)O is formed in the anodic electrochemical oxidation of formic acid/lithium formate. Using a [CoIIIW12O40]5- polyanion catalyst, this led to the formation of phenyl formate from benzene. Here, we present our studies into the reactivity of electrochemically in situ generated HC(O)O with organic substrates. Reactions with benzene and a selection of substituted derivatives showed that HC(O)O is mildly electrophilic according to both experimentally and computationally derived Hammett linear free energy relationships. The reactions of HC(O)O with terminal alkenes significantly favor anti-Markovnikov oxidations yielding the corresponding aldehyde as the major product as well as further oxidation products. Analysis of plausible reaction pathways using 1-hexene as a representative substrate favored the likelihood of hydrogen abstraction from the allylic C-H bond forming a hexallyl radical followed by strongly preferred further attack of a second HC(O)O radical at the C1 position. Further oxidation products are surmised to be mostly a result of two consecutive addition reactions of HC(O)O to the CC double bond. An outer-sphere electron transfer between the formyloxyl radical donor and the [CoIIIW12O40]5- polyanion acceptor forming a donor-acceptor [D+-A-] complex is proposed to induce the observed anti-Markovnikov selectivity. Finally, the overall reactivity of HC(O)O towards hydrogen abstraction was evaluated using additional substrates. Alkanes were only slightly reactive, while the reactions of alkylarenes showed that aromatic substitution on the ring competes with C-H bond activation at the benzylic position. C-H bonds with bond dissociation energies (BDE) ≤ 85 kcal mol-1 are easily attacked by HC(O)O and reactivity appears to be significant for C-H bonds with a BDE of up to 90 kcal mol-1. In summary, this research identifies the reactivity of HC(O)O towards radical electrophilic substitution of arenes, anti-Markovnikov type oxidation of terminal alkenes, and indirectly defines the activity of HC(O)O towards C-H bond activation.
- Iron, Mark A.,Khenkin, Alexander M.,Neumann, Ronny,Somekh, Miriam
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p. 11584 - 11591
(2020/11/23)
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- Exploiting Synergistic Catalysis for an Ambient Temperature Photocycloaddition to Pyrazoles
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Sydnone-based cycloaddition reactions are a versatile platform for pyrazole synthesis, however they operate under harsh conditions (high temperature and long reaction times). Herein we report a strategy that addresses this limitation utilizing the synergistic combination of organocatalysis and visible-light photocatalysis. This new approach proceeds under ambient conditions and with excellent levels of regiocontrol. Mechanistic studies suggest that photoactivation of sydnones, rather than enamines, is key to the successful implementation of this process.
- Lakeland, Christopher P.,Watson, David W.,Harrity, Joseph P. A.
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supporting information
p. 155 - 159
(2019/12/11)
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- Photochemical synthesis of acetals utilizing Schreiner's thiourea as the catalyst
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Acetalization of aldehydes is an area of great importance in Organic Chemistry for both synthetic and biological puproses. Herein, we report a mild, inexpensive and green photochemical protocol, where Schreiner's thiourea (N,N′-bis[3,5-bis(trifluoromethyl)-phenyl]-thiourea) is utilized as the catalyst and cheap household lamps as the light source. A variety of aromatic and aliphatic aldehydes were converted into acetals in good to high yields (23 examples, 36-96% yield) and an example of the synthesis of a cyclic acetal is provided. The reaction mechanism was also studied.
- Kokotos, Christoforos G.,Nikitas, Nikolaos F.,Spiliopoulou, Nikoleta
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supporting information
p. 3539 - 3545
(2020/06/25)
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- Chirality-Driven Mode of Binding of α-Aminophosphonic Acid-Based Allosteric Inhibitors of the Human Farnesyl Pyrophosphate Synthase (hFPPS)
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Thienopyrimidine-based allosteric inhibitors of the human farnesyl pyrophosphate synthase (hFPPS), characterized by a chiral α-aminophosphonic acid moiety, were synthesized as enantiomerically enriched pairs, and their binding mode was investigated by X-ray crystallography. A general consensus in the binding orientation of all (R)- and (S)-enantiomers was revealed. This finding is a prerequisite for establishing a reliable structure-activity relationship (SAR) model.
- Feng, Yuting,Park, Jaeok,Li, Shi-Guang,Boutin, Rebecca,Viereck, Peter,Schilling, Matthew A.,Berghuis, Albert M.,Tsantrizos, Youla S.
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p. 9691 - 9702
(2019/11/03)
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- Copper-Catalyzed Ring-Opening/Reconstruction of Anthranils with Oxo-Compounds: Synthesis of Quinoline Derivatives
-
A copper-catalyzed protocol for the construction of various 2-aryl(alkyl)-3-acylquinolines or 3-arylquinolines using readily available anthranils and 1,3-diketones or aldehydes as starting materials is reported herein. Dioxygen as the sole oxidant and hexafluoroisopropanol as the solvent play an important role in both procedures. This ring-opening/reconstruction strategy involving N-O bond cleavage and C-N/C-C bond formation features high yields and broad substrate scope.
- Zou, Liang-Hua,Zhu, Hao,Zhu, Shuai,Shi, Kai,Yan, Cheng,Li, Ping-Gui
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p. 12301 - 12313
(2019/10/11)
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- Homogeneous oxidation reactions catalysed by in situ-generated triazolylidene copper(I) complexes
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Abstract: Four new Cu complexes bearing triazolylidene ligands 1-(R)-3-methyl-4-phenyl-1H-1,2,3-triazol-3-ium-5-yl: R = phenyl (2a), mesitylenyl (2b), propyl (2c), hexyl (2d) (NHC) were synthesised in high yields. Characterisation by spectroscopic and analytical methods confirmed the molecular composition of the complexes as NHC–Cu-I. The complexes 2(a–d) bearing NHC wingtip variations were tested as in situ-generated catalysts for homogeneous oxidation catalysis with H2O2 as oxidant. The in situ technique was adopted for ease of application and to circumvent the poor stability of the complexes in solution. The results showed that the NHC–Cu-I complexes are capable of initiating oxidation reactions, yielding ketones/aldehydes as dominant products for the oxidation of alkanes under optimised reaction conditions, with complexes bearing aliphatic N-substituents showing the highest catalytic activities. Oxidation of toluene with 2c resulted in a mixture of benzaldehyde and benzyl alcohol as the main products. Also, 2c catalysed the oxidation of n-octane, yielding a mixture of mainly C-8 oxidation products with over 75% selectivity for the isomeric octanones. Analysis of regioselectivity indicated that the internal Csp3–H bonds of n-octane [especially C(2)] are more reactive than the terminal ones. Graphical abstract: [Figure not available: see fulltext.].
- Mncube, Siyabonga G.,Bala, Muhammad D.
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p. 145 - 151
(2018/10/26)
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- SUBSTITUTED AMINOTHIAZOLES AS INHIBITORS OF NUCLEASES
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The invention provides compounds represented by the structural formula (1): wherein R1, R2, R3, R4, R5, R6 are as defined in the claims. The compounds are inhibitors of nucleases, and are useful in particular in a method of treatment and/or prevention of proliferative diseases, neurodegenerative diseases, and other genomic instability associated diseases.
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Page/Page column 14; 26-27
(2019/11/12)
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- Carbon chain shape selectivity by the mouse olfactory receptor OR-I7
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The rodent OR-I7 is an olfactory receptor exemplar activated by aliphatic aldehydes such as octanal. Normal alkanals shorter than heptanal bind OR-I7 without activating it and hence function as antagonists in vitro. We report a series of aldehydes designed to probe the structural requirements for aliphatic ligand chains too short to meet the minimum approximate 6.9 ? length requirement for receptor activation. Experiments using recombinant mouse OR-I7 expressed in heterologous cells show that in the context of short aldehyde antagonists, OR-I7 prefers binding aliphatic chains without branches, though a single methyl on carbon-3 is permitted. The receptor can accommodate a surprisingly large number of carbons (e.g. ten in adamantyl) as long as the carbons are part of a conformationally constrained ring system. A rhodopsin-based homology model of mouse OR-I7 docked with the new antagonists suggests that small alkyl branches on the alkyl chain sterically interfere with the hydrophobic residues lining the binding site, but branch carbons can be accommodated when tied back into a compact ring system like the adamantyl and bicyclo[2.2.2]octyl systems.
- Liu, Min Ting,Ho, Jianghai,Liu, Jason Karl,Purakait, Radhanath,Morzan, Uriel N.,Ahmed, Lucky,Batista, Victor S.,Matsunami, Hiroaki,Ryan, Kevin
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supporting information
p. 2541 - 2548
(2018/04/12)
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- TRICYCLIC COMPOUND SERVING AS IMMUNOMODULATOR
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Provided are compounds of formula I and formula II or pharmaceutically acceptable salts of the compounds and pharmaceutical compositions thereof. The compounds of formula I and formula II or the pharmaceutically acceptable salts of the compounds provide indole 2,3-dioxygenase (IDO) inhibitory activity and are capable of treating IDO-mediated immunosuppressive diseases, such as infectious diseases or cancer.
- -
-
Paragraph 0262-0263
(2019/01/04)
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- Spin-Center Shift-Enabled Direct Enantioselective α-Benzylation of Aldehydes with Alcohols
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Nature routinely engages alcohols as leaving groups, as DNA biosynthesis relies on the removal of water from ribonucleoside diphosphates by a radical-mediated "spin-center shift" (SCS) mechanism. Alcohols, however, remain underused as alkylating agents in synthetic chemistry due to their low reactivity in two-electron pathways. We report herein an enantioselective α-benzylation of aldehydes using alcohols as alkylating agents based on the mechanistic principle of spin-center shift. This strategy harnesses the dual activation modes of photoredox and organocatalysis, engaging the alcohol by SCS and capturing the resulting benzylic radical with a catalytically generated enamine. Mechanistic studies provide evidence for SCS as a key elementary step, identify the origins of competing reactions, and enable improvements in chemoselectivity by rational photocatalyst design.
- Nacsa, Eric D.,MacMillan, David W. C.
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supporting information
p. 3322 - 3330
(2018/03/13)
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- Enantioselective Bromolactonization of Trisubstituted Olefinic Acids Catalyzed by Chiral Pyridyl Phosphoramides
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Enantioselective bromolactonization of trisubstituted olefinic acids producing synthetically useful chiral lactones with two contiguous asymmetric centers has remained mainly unexplored except for the 6-exo cyclization mode. In this work, the 5-exo- and 6
- Nishikawa, Yasuhiro,Hamamoto, Yuhta,Satoh, Rika,Akada, Naho,Kajita, Shuhei,Nomoto, Marina,Miyata, Megumi,Nakamura, Madoka,Matsubara, Chinatsu,Hara, Osamu
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supporting information
p. 18880 - 18885
(2018/12/04)
-
- α-Tetrasubstituted Aldehydes through Electronic and Strain-Controlled Branch-Selective Stereoselective Hydroformylation
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Hydroformylation utilizes dihydrogen, carbon monoxide, and a catalyst to transform alkenes into aldehydes. This work applies chiral bisdiazaphospholane (BDP)- and bisphospholanoethane-ligated rhodium complexes to the hydroformylation of a variety of alkenes to produce chiral tetrasubstituted aldehydes. 1,1′-Disubstituted acrylates bearing electron-withdrawing substituents undergo hydroformylation under mild conditions (1 mol % of catalyst/BDP ligand, 150 psig gas, 60 °C) with high conversions and yields of tetrasubstituted aldehydes (e.g., 13:1 regioselectivity, 85% ee, and 99% regioselectivity and >19:1 diastereoselectivity to tetrasubstituted aldehydes at rates >50 catalyst turnovers/hour. NMR studies of the noncatalytic reaction of HRh(BDP)(CO)2 with methyl 1-fluoroacrylate enable interception of tertiary alkylrhodium intermediates, demonstrating migratory insertion to acyl species is slower than formation of secondary and primary alkylrhodium intermediates. Overall, these investigations reveal how the interplay of sterics, electronics, and ring strain are harnessed to provide access to valuable α-tetrasubstituted aldehyde synthetic building blocks by promoting branched-selective hydroformylation.
- Eshon, Josephine,Foarta, Floriana,Landis, Clark R.,Schomaker, Jennifer M.
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p. 10207 - 10220
(2018/09/06)
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- SeO2-Mediated One-Pot Synthesis of 3-Cyanofurans from 3-Oxo-3-arylpropanenitriles and Substituted Acetaldehydes
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An SeO2-mediated one-pot method was established for the synthesis of 3-cyanofurans from 3-oxo-3-arylpropanenitriles and substituted acetaldehydes. The generality of the reaction was explored, and a plausible mechanism is proposed.
- Zhou, Jie,Zhu, Xinhai,Huang, Manna,Wan, Yiqian
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supporting information
p. 2317 - 2321
(2017/05/01)
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- One-Pot Preparation of C1-Homologated Aliphatic Nitriles from Aldehydes through a Wittig Reaction under Metal-Cyanide-Free Conditions
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A one-pot protocol to obtain C1-homologated aliphatic nitriles was achieved by treating aromatic and aliphatic aldehydes with the (methoxymethyl)triphenylphosphonium ylide followed by hydrolysis of the resulting methyl vinyl ethers with pTsOH (Ts = para-toluenesulfonyl) and treatment with molecular iodine and aqueous ammonia under metal cyanide free conditions. Neopentyl-type nitriles, which could not be obtained by conventional methods that involved conversion of the neopentyl alcohol into a tosylate and treatment with metal cyanide, were successfully obtained by using the present method.
- Ezawa, Masatoshi,Togo, Hideo
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p. 2379 - 2384
(2017/05/01)
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- NRF2 REGULATORS
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Provided are aryl analogs，pharmaceutical compositions containing them and their use as NRF2 regulators.
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Page/Page column 330
(2017/01/02)
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- Non-plasmonic metal nanoparticles as visible light photocatalysts for the selective oxidation of aliphatic alcohols with molecular oxygen at near ambient conditions
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Nanoparticles (NPs) of Pd and Pt were used for the selective oxidation of aliphatic alcohols with molecular oxygen as an oxidant at near ambient temperatures under visible light irradiation. Distinct final products were obtained under identical reaction conditions, aliphatic esters formed over the Pd NPs while aldehydes formed over the Pt NPs. The reason for this different product selectivity is proven to be due to the much stronger interaction of Pd NPs with alcohol and aldehyde compared to Pt NPs. The photocatalytic activity is tuneable by light intensity or a moderate change in the reaction temperature.
- Tana, Tana,Guo, Xiao-Wei,Xiao, Qi,Huang, Yiming,Sarina, Sarina,Christopher, Phillip,Jia, Jianfeng,Wu, Haishun,Zhu, Huaiyong
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p. 11567 - 11570
(2016/10/03)
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- Expedient Access to 2,3-Dihydropyridines from Unsaturated Oximes by Rh(III)-Catalyzed C-H Activation
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α,β-Unsaturated oxime pivalates are proposed to undergo reversible C(sp2)-H insertion with cationic Rh(III) complexes to furnish five-membered metallacycles. In the presence of 1,1-disubstituted olefins, these species participate in irreversible migratory insertion to give, after reductive elimination, 2,3-dihydropyridine products in good yields. Catalytic hydrogenation can then be used to convert these molecules into piperidines, which are important structural components of numerous pharmaceuticals.
- Romanov-Michailidis, Fedor,Sedillo, Kassandra F.,Neely, Jamie M.,Rovis, Tomislav
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supporting information
p. 8892 - 8895
(2015/08/03)
-
- Organomediated Enantioselective 18F Fluorination for PET Applications
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The first organomediated asymmetric 18F fluorination has been accomplished using a chiral imidazolidinone and [18F]N-fluorobenzenesulfonimide. The method provides access to enantioenriched 18F-labeled α-fluoroaldehydes (>90 % ee), which are versatile chiral 18F synthons for the synthesis of radiotracers. The utility of this process is demonstrated with the synthesis of the PET (positron emission tomography) tracer (2S,4S)-4-[18F]fluoroglutamic acid.
- Buckingham, Faye,Kirjavainen, Anna K.,Forsback, Sarita,Krzyczmonik, Anna,Keller, Thomas,Newington, Ian M.,Glaser, Matthias,Luthra, Sajinder K.,Solin, Olof,Gouverneur, Véronique
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supporting information
p. 13366 - 13369
(2015/11/09)
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- Stereoconvergent negishi arylations of racemic secondary alkyl electrophiles: Differentiating between a CF3 and an alkyl group
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In this report, we establish that a readily available nickel/bis(oxazoline) catalyst accomplishes a wide array of enantioconvergent cross-couplings of arylzinc reagents with CF3-substituted racemic secondary alkyl halides, a process that necessitates that the chiral catalyst be able to effectively distinguish between a CF3 and an alkyl group in order to provide good ee. We further demonstrate that this method can be applied without modification to the catalytic asymmetric synthesis of other families of fluorinated organic compounds.
- Liang, Yufan,Fu, Gregory C.
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supporting information
p. 9523 - 9526
(2015/08/18)
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- Enantioselective α-Alkylation of Aldehydes by Photoredox Organocatalysis: Rapid Access to Pharmacophore Fragments from β-Cyanoaldehydes
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The combination of photoredox catalysis and enamine catalysis has enabled the development of an enantioselective α-cyanoalkylation of aldehydes. This synergistic catalysis protocol allows for the coupling of two highly versatile yet orthogonal functionalities, allowing rapid diversification of the oxonitrile products to a wide array of medicinally relevant derivatives and heterocycles. This methodology has also been applied to the total synthesis of the lignan natural product (-)-bursehernin. A combination of photoredox catalysis and enamine catalysis has enabled the development of an enantioselective cyanoalkylation of aldehydes. This synergistic catalysis protocol makes possible the coupling of two highly versatile yet orthogonal functionalities.
- Welin, Eric R.,Warkentin, Alexander A.,Conrad, Jay C.,MacMillan, David W. C.
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supporting information
p. 9668 - 9672
(2015/08/11)
-
- Flexible, phase-transfer catalyzed approaches to 4-substituted prolines
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A range of 4-substituted prolines can be rapidly synthesized from a protected glycine Schiff base in only four steps and in 27-55% overall yield. Phase transfer catalysis allows direct access to both enantiomeric series, and the relative stereochemistry at the 4-position is readily controlled (>10:1 dr) through the choice of hydrogenation conditions.
- Johnston, Heather J.,McWhinnie, Fergus S.,Landi, Felicetta,Hulme, Alison N.
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supporting information
p. 4778 - 4781
(2015/04/27)
-
- Broad-spectrum catalysts for the ambient temperature anti-Markovnikov hydration of alkynes
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Anti-Markovnikov alkyne hydration provides a valuable route to aldehydes. Half-sandwich ruthenium complexes ligated by 5,5′-bis(trifluoromethyl)-2, 2′-bipyridine are remarkably active for this transformation. In the presence of 2 mol % metal, a wide range of functionalized aliphatic and aromatic alkynes are hydrated in high yield at ambient temperature. Alkyne hydration: Half-sandwich ruthenium complexes derived from 5,5′-bis(trifluoromethyl)- 2,2′-bipyridine show a high activity for the anti-Markovnikov hydration of terminal alkynes (see picture). A wide array of alkynes are efficiently hydrated to aldehydes using 2 mol % metal loadings at 25 °C within 8-24 h.
- Li, Le,Zeng, Mingshuo,Herzon, Seth B.
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supporting information
p. 7892 - 7895
(2014/08/05)
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- CARBOXAMIDE OR SULFONAMIDE SUBSTITUTED THIAZOLES AND RELATED DERIVATIVES AS MODULATORS FOR THE ORPHAN NUCLEAR RECEPTOR ROR[GAMMA]
-
The invention provides modulators for the orphan nuclear receptor RORy and methods for treating RORy mediated diseases by administering these novel RORy modulators to a human or a mammal in need thereof. Specifically, the present invention provides carboxamide or sulfonamide containing cyclic compounds of Formula (1), (1'), (100), (100'), (200) and (200') and the enantiomers, diastereomers, tautomers, /V-oxides, solvates and pharmaceutically acceptable salts thereof.
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Page/Page column 180; 181
(2014/01/07)
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- Catalytic, enantioselective, and highly chemoselective bromocyclization of olefinic dicarbonyl compounds
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Overriding preferences: An amine-thiocarbamate catalyst can mediate the facile, efficient, and highly enantioselective bromocyclization of olefinic 1,3-dicarbonyl compounds. In the presence of the bifunctional catalyst, the bromination occurs chemoselectively at the olefinic moiety rather than at the carbon atom in the α-position to the carbonyl units. Copyright
- Zhao, Yi,Jiang, Xiaojian,Yeung, Ying-Yeung
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supporting information
p. 8597 - 8601
(2013/09/12)
-
- Biocatalytic production of tetrahydroisoquinolines
-
The promiscuity of the enzyme norcoclaurine synthase is described. This biocatalyst yielded a diverse array of substituted tetrahydroisoquinolines by cyclizing dopamine with various acetaldehydes in a Pictet-Spengler reaction. This enzymatic reaction may provide a biocatalytic route to a range of tetrahydroisoquinoline alkaloids.
- Ruff, Bettina M.,Br?se,O'Connor, Sarah E.
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supporting information; experimental part
p. 1071 - 1074
(2012/03/27)
-
- Modified polyacrylamide-supported chlorochromate as a new polymeric oxidizing agent
-
Modified polyacrylamide-supported chlorochromate was synthesized and used as a versatile and efficient oxidizing agent for the oxidation of various organic compounds, such as hydroxyl compounds, silylethers, oximes, thiols, and others. Over oxidation of the products (aldehydes to carboxylic acids) was not observed with this oxidizing agent. The oxidant was insoluble in the oxidation media and the chromium(VI) ions remained firmly bound to the insoluble polymeric support after the oxidation reaction. The mild reaction condition, easy work-up, short reaction times, regenerability of the reagent and its easy preparation and handling are among the advantages of this new polymeric chlorochromate reagent. 2012 Copyright (CC) SCS.
- Tamami, Bahman,Heiran, Roghayeh,Montazer, Elham Riazi
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p. 685 - 697
(2012/10/29)
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- A remarkably simple α-oximation of aldehydes via organo-SOMO catalysis
-
A novel α-oximation reaction of unactivated aldehydes has been achieved in excellent yields by reaction with NaNO2-FeCl3 couple and in the presence of pyrrolidine as organocatalyst.
- Gentili, Patrizia,Pedetti, Silvia
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supporting information; experimental part
p. 5358 - 5360
(2012/06/30)
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- An iron catalyzed regioselective oxidation of terminal alkenes to aldehydes
-
Fe(BF4)2·6H2O with pyridine-2,6-dicarboxylic acid and PhIO can efficiently catalyze the regioselective oxidation of terminal alkene derivatives to aldehydes under mild and benign reaction conditions.
- Chowdhury, Abhishek Dutta,Ray, Ritwika,Lahiri, Goutam Kumar
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supporting information; experimental part
p. 5497 - 5499
(2012/07/01)
-
- HETEROCYCLIC COMPOUNDS AS JANUS KINASE INHIBITORS
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The invention provides compounds of formula (I) or a salt thereof as described herein. The invention also provides pharmaceutical compositions comprising a compound of formula (I), processes for preparing compounds of formula (I), intermediates useful for preparing compounds of formula I and therapeutic methods for suppressing an immune response or treating cancer or a hematologic malignancy using compounds of formula (I).
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Page/Page column 163
(2011/04/18)
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- Microwave-assisted synthesis of 5-substituted 2-aminothiophenes starting from arylacetaldehydes
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An easy three-step pathway for the synthesis of arylacet-aldehydes from the corresponding carboxylic acids in very high yields is described. Their use as precursors of 5-substituted-2-aminothiophenes is illustrated via a microwave-assisted Gewald reaction. This method allows obtaining the expected compounds in a shorter time and with better yields and purities than the classical procedures. Georg Thieme Verlag Stuttgart - New York.
- Revelant, Germain,Dunand, Sandrine,Hesse, Stephanie,Kirsch, Gilbert
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experimental part
p. 2935 - 2940
(2011/11/01)
-
- GAMMA AMINO ACID BUILDING BLOCKS
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The invention provides compounds and methods, for example, to carry out organocatalytic Michael additions of aldehydes to cyclically constrained nitroethylene compounds catalyzed by a pro line derivative to provide cyclically constrained α-substituted-γ-n
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Page/Page column 36
(2011/05/05)
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- Discovery of novel thieno[2,3-d]pyrimidin-4-yl hydrazone-based cyclin-dependent kinase 4 inhibitors: synthesis, biological evaluation and structure-activity relationships
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The design, synthesis, and evaluation of novel thieno[2,3-d]pyrimidin-4-yl hydrazone analogues as cyclin-dependent kinase 4 (CDK4) inhibitors are described. In continuing our program aim to search for potent CDK4 inhibitors, the introduction of a thiazole group at the hydrazone part has led to marked enhancement of chemical stability. Furthermore, by focusing on the optimization at the C-4′ position of the thiazole ring and the C-6 position of the thieno[2,3-d]pyrimidine moiety, compound 35 has been identified with efficacy in a xenograft model of HCT116 cells. In this paper, the potency, selectivity profile, and structure-activity relationships of our synthetic compounds are discussed.
- Horiuchi, Takao,Takeda, Yasuyuki,Haginoya, Noriyasu,Miyazaki, Masaki,Nagata, Motoko,Kitagawa, Mayumi,Akahane, Kouichi,Uoto, Kouichi
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experimental part
p. 991 - 1002
(2011/10/02)
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- Efficient, solvent-free and rapid oxidation of alcohols to carbonyl compounds with N,N'-dibromo-N,N'-1,2-ethanediylbis(benzene sulfonamide)
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N,N'-Dibromo-N,N'-1,2-ethanediylbis(benzene sulfonamide) (BNBBS): a safe, neutral and efficient reagent was utilized for the rapid and selective oxidation of alcohols to carbonyl compounds with no side reactions such as oxidations of carbon-hydrogen bonds, over oxidation of aldehydes and bromination of aromatic rings; under solvent-free condition, at room temperature with excellent yield.
- Mahboubifar,Khazaei,Rostami
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experimental part
p. 829 - 831
(2011/12/22)
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- Enantioselective linchpin catalysis by SOMO catalysis: An approach to the asymmetric a-chlorination of aldehydes and terminal epoxide formation
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Time for SOme MOre: For the first time SOMO (singly occupied molecular orbital) activation has been exploited to allow a new approach to the α-chlorination of aldehydes. This transformation can be readily implemented as part of a linchpin catalysis approach to the enantioselective production of terminal epoxides.
- Amatore, Muriel,Beeson, Teresa D.,Brown, Sean P.,MacMillan, David W. C.
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supporting information; experimental part
p. 5121 - 5124
(2009/12/07)
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- Stereospecific synthesis of conformationally constrained γ-amino acids: New foldamer building blocks that support helical secondary structure
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(Figure Presented) A highly stereoselective synthesis of novel cyclically constrained γ-amino acid residues is presented. The key step involves organocatalytic Michael addition of an aldehyde to 1-nitrocyclohexene. After aldehyde reduction, this approach provides optically active β-substituted δ-nitro alcohols (96-99% ee), which can be converted to γ-amino acid residues with a variety of substituents at the α position. We have used these new building blocks to prepare α/γ-peptide foldamers that adopt a specific helical conformation in solution and in the solid state. Copyright
- Guo, Li,Chi, Yonggui,Almeida, Aaron M.,Guzei, Ilia A.,Parker, Brian K.,Gellman, Samuel H.
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supporting information; experimental part
p. 16017 - 16020
(2010/02/15)
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- Iridium-catalyzed isomerization of primary allylic alcohols under mild reaction conditions
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The isomerization of primary allylic alcohols into the corresponding aldehydes has been accomplished using an analogue of Crabtree's iridium hydrogenation catalyst and by adequately tuning the experimental conditions. A wide range of substrates is converted quantitatively into the desired aldehyde at room temperature in expedient reaction times by using catalyst loading as low as 0.25 mol %.
- Mantilli, Luca,Mazet, Clément
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scheme or table
p. 4141 - 4144
(2009/12/01)
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- Iridium-catalyzed isomerization of primary allylic alcohols
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A readily accessible iridium hydrogenation catalyst displays high reactivity for the isomerization of primary allylic alcohols under mild reaction conditions. Key to the efficiency of the catalytic system is to deviate from the conventional hydrogenation route in favor of the desired isomerization pathway by adequately tuning the reaction conditions as indicated by preliminary mechanistic investigations. Schweizerische Chemische Gesellschaft.
- Mantilli, Luca,Mazet, Clement
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scheme or table
p. 35 - 37
(2010/03/30)
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- Assessing synthetic strategies: Total syntheses of (±)- neodolabellane-type diterpenoids
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Two strategies, namely a cross-metathesis/ring-closing metathesis and Pd-catalyzed Stille allylation/Nozaki-Hiyama-Kishi coupling, are examined for the preparation of neodolabellane-type diterpenoids 1 and 2. Whereas the first approach possessed synthetic
- Valente, Cory,Organ, Michael G.
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supporting information; experimental part
p. 8239 - 8245
(2009/09/29)
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- Oxidative rearrangements of isobenzofurans: Studies toward the synthesis of the ajudazols
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(Chemical Equation Presented) We present a new facet of isobenzofuran chemistry which allows for its efficient manipulation to generate biologically relevant entities. This methodology has been successfully applied toward the synthesis of ajudazol A.
- Hobson, Stephen J.,Parkin, Andrew,Marquez, Rodolfo
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supporting information; experimental part
p. 2813 - 2816
(2009/05/27)
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- NOVEL COMPOUNDS AS CANNABINOID RECEPTOR LIGANDS
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The present application relates to thiazolylidene containing compounds of formula (I) wherein R1, R2, R3, R4, L2 and A are as defined in the specification. Compositions comprising such compounds, and methods for treating conditions and disorders using such compounds and compositions are also disclosed.
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Page/Page column 67
(2008/12/07)
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- Synthetic applications of synergism using catalytic binuclear elimination reactions. Further examples of rhodium-manganese and rhodium-rhenium-catalyzed hydroformylations
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Synergism has been previously observed in both rhodium-manganese-and rhodium-rhenium-catalyzed hydroformylation. Furthermore, detailed in situ spectroscopic investigations have conclusively shown that the phenomenological origin of this synergistic effect is catalytic binuclear elimination (J. Am. Chem. Soc. 2003, 125, 5540-5548; 2007, 129, 13327-13334). In the present contribution, further substrates are used in the hydroformylation reaction with both rhodium-manganese and rhodium-rhenium. In situ spectroscopic studies show that (i) significant rate enhancements occur in the mixed metal systems with the new substrates and (ii) the organometallics present in the active systems, and their concentration profiles are consistent with those present in the previouslystud ied catalytic binuclear elimination reactions (CBER). It is therefore concluded that catalytic binuclear elimination is a rather general mechanism in mixed metal hydroformylations and is rather independent of the substrates used. Further discussion is given to mechanistic aspects, synthetic efficiency, and the possibility that such synergistic effects might be useful to other classes of organic syntheses.
- Li, Chuanzhao,Chen, Li,Garland, Marc
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body text
p. 679 - 690
(2009/04/12)
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- SOLUBLE EPOXIDE HYDROLASE INHIBITORS
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Disclosed are alpha keto amide and alpha hydroxy amide compounds and compositions that inhibit soluble epoxide hydrolase (sEH), methods for preparing the compounds and compositions, and methods for treating patients with such compounds and compositions. The compounds, compositions, and methods are useful for treating a variety of sEH mediated diseases, including hypertensive, cardiovascular, inflammatory, pulmonary, and diabetic-related diseases.
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Page/Page column 93; 94
(2008/12/06)
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- NOVEL COMPOUNDS AS CANNABINOID RECEPTOR LIGANDS AND USES THEREOF
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The present invention relates to compounds of formula (I), or pharmaceutically acceptable salts, prodrugs, salts of prodrugs, or combinations thereof, wherein R1, R2, R3, R4, and L2, are defined in th
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Page/Page column 128
(2008/06/13)
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- Diacylglycerol acyltransferase inhibitors
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Provided herein are compounds of the formula (I): as well as pharmaceutically acceptable salts thereof, wherein the substituents are as those disclosed in the specification. These compounds, and the pharmaceutical compositions containing them, are useful for the treatment of diseases such as, for example, obesity, type II diabetes mellitus and metabolic syndrome.
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Page/Page column 28
(2010/11/27)
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- PYRAZOLO[3,4-c]QUINOLINES, PYRAZOLO[3,4-c]NAPHTHYRIDINES, ANALOGS THEREOF, AND METHODS
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Pyrazolo[3,4-c]quinolines, pyrazolo[4,5-c]naphthyridines, and analogs thereof, eg., 6,7,8,9-tetrahydro pyrazolo[3,4-c]quinolines, and, pharmaceutical compositions containing the compounds, intermediates, methods of making these compounds, and methods of use of these compounds as immunomodulators, for inhibiting cytokine biosynthesis in animals and in the therapeutic or prophylactic treatment of diseases by inhibiting cytokine biosynthesis are disclosed.
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Page/Page column 60
(2008/06/13)
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