- A Cooperative Ternary Catalysis System for Asymmetric Lactonizations of α-Ketoesters
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A general and enantioselective N-heterocyclic carbene (NHC)-catalyzed lactonization of simple enals and α-ketoesters has been discovered using a new ternary cooperative catalytic system. The highly selective annulation was achieved by using a combination of a chiral NHC, a hydrogen-bond donor, and a metal salt, facilitating self-assembly of the reactive partners. A proposed model for this new mode of NHC chiral relay catalysis is supported by experimental and computational mechanistic studies. (Figure presented.).
- Murauski, Kathleen J. R.,Walden, Daniel M.,Cheong, Paul Ha-Yeon,Scheidt, Karl A.
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- C?H Insertion as a Key Step to Spiro-Oxetanes, Scaffolds for Drug Discovery
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A new route to spiro-oxetanes, potential scaffolds for drug discovery, is described. The route is based on the selective 1,4-C?H insertion reactions of metallocarbenes, generated from simple carbonyl precursors in flow or batch mode, to give spiro-β-lacto
- Nicolle, Simon M.,Nortcliffe, Andrew,Bartrum, Hannah E.,Lewis, William,Hayes, Christopher J.,Moody, Christopher J.
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Read Online
- Crystallization-induced diastereomer transformation of thiohydantoin derivatives
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Crystallization-induced diastereomer transformation of valuable thiohydantoin derivatives was developed for the first time. Three thiohydantoins synthesized from three (R)-N-phenethylthioureas and benzoylformyl chloride were obtained as diasteromeric mixt
- Mino, Takashi,Sakamoto, Masami,Uemura, Naohiro,Yoshida, Yasushi
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- A photo-auxiliary approach - enabling excited state classical phototransformations with metal free visible light irradiation
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Most traditional photoreactions require UV light to yield the desired product. To address this issue, photoreaction of hydrazide based chromophores was evaluated with visible light using a metal free photocatalyst to afford photoproducts in high yields. This hydrazide functionality itself may be removed/modified after the photoreaction, highlighting its role as a “photo-auxiliary”. A preliminary mechanistic model based on photophysical experiments is provided to highlight the generality of the strategy.
- Iyer, Akila,Jockusch, Steffen,Sivaguru, Jayaraman
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Read Online
- Novel positive allosteric modulators of A2B adenosine receptor acting as bone mineralisation promoters
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Small-molecules acting as positive allosteric modulators (PAMs) of the A2B adenosine receptor (A2B AR) could potentially represent a novel therapeutic strategy for pathological conditions characterised by altered bone homeostasis, including osteoporosis. We investigated a library of compounds (4-13) exhibiting different degrees of chemical similarity with three indole derivatives (1-3), which have been recently identified by us as PAMs of the A2B AR able to promote mesenchymal stem cell differentiation and bone formation. Evaluation of mineralisation activity of 4-13 in the presence and in the absence of the agonist BAY60-6583 allowed the identification of lead compounds with therapeutic potential as anti-osteoporosis agents. Further biological characterisation of one of the most performing compounds, the benzofurane derivative 9, confirmed that such a molecule behaves as PAM of the A2B AR.
- Barresi, Elisabetta,Giacomelli, Chiara,Marchetti, Laura,Baglini, Emma,Salerno, Silvia,Greco, Giovanni,Da Settimo, Federico,Martini, Claudia,Trincavelli, Maria Letizia,Taliani, Sabrina
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p. 286 - 294
(2020/12/22)
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- Non-Bonding 1,4-Sulphur-Oxygen Interaction Governs the Reactivity of α-Ketothioesters in Triphenylphosphine-Catalyzed Cyclization with Acetylenedicarboxylates
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α-Ketothioesters undergo triphenylphosphine (PPh3)-catalyzed cyclization with acetylenedicarboxylate esters smoothly, in contrast to α-ketooxoesters which require more drastic conditions with the limited substrate scope. The reaction works well
- Bankura, Abhijit,Saha, Jayanta,Maity, Rajib,Das, Indrajit
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supporting information
p. 1014 - 1021
(2020/12/31)
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- Diversification of α-ketoamides: Via transamidation reactions with alkyl and benzyl amines at room temperature
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A wide range of N-tosyl α-ketoamides underwent transamidation with various alkyl amines in the absence of a catalyst, base, or additive. On the other hand, transamidation in N-Boc α-ketoamides was achieved in the presence of Cs2CO3. The reactions proceede
- Junaid, Qazi Mohammad,Kandasamy, Jeyakumar,Popuri, Sureshbabu,Sabiah, Shahulhameed,Singh, Shweta
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p. 7134 - 7140
(2021/08/30)
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- Synthesis of N-trifluoromethyl amides from carboxylic acids
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Found in biomolecules, pharmaceuticals, and agrochemicals, amide-containing molecules are ubiquitous in nature, and their derivatization represents a significant methodological goal in fluorine chemistry. Trifluoromethyl amides have emerged as important functional groups frequently found in pharmaceutical compounds. To date, there is no strategy for synthesizing N-trifluoromethyl amides from abundant organic carboxylic acid derivatives, which are ideal starting materials in amide synthesis. Here, we report the synthesis of N-trifluoromethyl amides from carboxylic acid halides and esters under mild conditions via isothiocyanates in the presence of silver fluoride at room temperature. Through this strategy, isothiocyanates are desulfurized with AgF, and then the formed derivative is acylated to afford N-trifluoromethyl amides, including previously inaccessible structures. This method shows broad scope, provides a platform for rapidly generating N-trifluoromethyl amides by virtue of the diversity and availability of both reaction partners, and should find application in the modification of advanced intermediates.
- Flavell, Robert R.,Liu, Jianbo,Parker, Matthew F. L.,Toste, F. Dean,Wang, Sinan,Wilson, David M.
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supporting information
p. 2245 - 2255
(2021/08/12)
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- Stereoselective [4+2]-Cycloaddition with Chiral Alkenylboranes
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A method for the stereoselective [4+2]-cycloaddition of alkenylboranes and dienes is presented. This transformation was accomplished through the introduction of a new strategy that involves the use of chiral N-protonated alkenyl oxazaborolidines as dieneophiles. The reaction leads to the formation of products that can be readily derivatized to more complex structural motifs through stereospecific transformations of the C?B bond such as oxidation and homologation. Detailed computation evaluation of the reaction has uncovered a surprising role of the counterion on stereoselectivity.
- Brown, M. Kevin,Houk, K. N.,Ni, Dongshun,Witherspoon, Brittany P.,Zhang, Hong,Zhou, Chen
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supporting information
p. 11432 - 11439
(2020/05/18)
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- Carbene-Catalyzed Enantioselective Aromatic N-Nucleophilic Addition of Heteroarenes to Ketones
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The aromatic nitrogen atoms of heteroarylaldehydes are activated by carbene catalysts to react with ketone electrophiles. Multi-functionalized cyclic N,O-acetal products are afforded in good to excellent yields and optical purities. Our reaction involves the formation of an unprecedented aza-fulvene-type acylazolium intermediate. A broad range of N-heteroaromatic aldehydes and electron-deficient ketone substrates works effectively in this transformation. Several of the chiral N,O-acetal products afforded through this protocol exhibit excellent antibacterial activities against Ralstonia solanacearum (Rs) and are valuable in the development of novel agrichemicals for plant protection.
- Liu, Yonggui,Luo, Guoyong,Yang, Xing,Jiang, Shichun,Xue, Wei,Chi, Yonggui Robin,Jin, Zhichao
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supporting information
p. 442 - 448
(2019/11/25)
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- Structure–activity relationships (SARs) of α- ketothioamides as inhibitors of phosphoglycerate dehydrogenase (PHGDH)
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For many years now, targeting deregulation within cancer cells’ metabolism has appeared as a promising strategy for the development of more specific and efficient cancer treatments. Recently, numerous reports highlighted the crucial role of the serine synthetic pathway, and particularly of the phosphoglycerate dehydrogenase (PHGDH), the first enzyme of the pathway, to sustain cancer progression. Yet, because of very weak potencies usually in cell-based settings, the inhibitors reported so far failed to lay ground on the potential of this approach. In this paper, we report a structure–activity relationship study of a series of α-ketothioamides that we have recently identified. Interestingly, this study led to a deeper understanding of the structure–activity relationship (SAR) in this series and to the identification of new PHGDH inhibitors. The activity of the more potent compounds was confirmed by cellular thermal shift assays and in cell-based experiments. We hope that this research will eventually provide a new entry point, based on this promising chemical scaffold, for the development of therapeutic agents targeting PHGDH.
- Spillier, Quentin,Ravez, Séverine,Unterlass, Judith,Corbet, Cyril,Degavre, Charline,Feron, Olivier,Frédérick, Rapha?l
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- Fluorogenic Enzyme-Triggered Domino Reactions Producing Quinoxalin-2(1 H)-one-based Heterocycles
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A simple and effective biocompatible domino reaction triggered by a model protease and leading to the formation of strongly fluorescent quinoxalin-2(1H)-one N-heterocycles is described. Some positive attributes including versatility and the ability to pro
- Bonnin, Quentin,Chevalier, Arnaud,Dejouy, Garance,Michaudet, Cédric,Picquet, Michel,Renault, Kévin,Romieu, Anthony,Valverde, Ibai E.
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supporting information
p. 6494 - 6499
(2020/09/02)
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- Visible-Light-Enabled Paternò-Büchi Reaction via Triplet Energy Transfer for the Synthesis of Oxetanes
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One of the most efficient ways to synthesize oxetanes is the light-enabled [2 + 2] cycloaddition reaction of carbonyls and alkenes, referred to as the Paternò-Büchi reaction. The reaction conditions for this transformation typically require the use of hig
- Rykaczewski, Katie A.,Schindler, Corinna S.
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supporting information
p. 6516 - 6519
(2020/09/02)
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- Isothiourea-Catalyzed Acylative Kinetic Resolution of Tertiary α-Hydroxy Esters
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A highly enantioselective isothiourea-catalyzed acylative kinetic resolution (KR) of acyclic tertiary alcohols has been developed. Selectivity factors of up to 200 were achieved for the KR of tertiary alcohols bearing an adjacent ester substituent, with both reaction conversion and enantioselectivity found to be sensitive to the steric and electronic environment at the stereogenic tertiary carbinol centre. For more sterically congested alcohols, the use of a recently-developed isoselenourea catalyst was optimal, with equivalent enantioselectivity but higher conversion achieved in comparison to the isothiourea HyperBTM. Diastereomeric acylation transition state models are proposed to rationalize the origins of enantiodiscrimination in this process. This KR procedure was also translated to a continuous-flow process using a polymer-supported variant of the catalyst.
- Greenhalgh, Mark D.,Laina-Martín, Víctor,Neyyappadath, Rifahath M.,Qu, Shen,Smith, Andrew D.,Smith, Samuel M.
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supporting information
p. 16572 - 16578
(2020/09/09)
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- Imidazole oxime ester compound, preparation method, composition and use thereof (by machine translation)
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The invention relates to novel imidazole oxime ester compound, preparation method, composition and in photoinitiators, photosensitizers, the light absorbent, or sensitizers of the application. The invention imidazole oxime ester compound, at the same time with imidazole kind of light initiator (for example BCIM) and oxime mere initiator (for example 0 XE - 1) structural features. In one aspect, the compounds of the invention has improved the imidazole kind of light will produce sludge to the shortcoming of the initiator. On the other hand, compound of the present invention improved the thermal stability of the oxime [...] initiator problem not good, and increasing the operating convenience. (by machine translation)
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Paragraph 0103-0106
(2019/05/11)
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- One-pot activation-alkynylation-cyclization synthesis of 1,5-diacyl-5-hydroxypyrazolines in a consecutive three-component fashion
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A consecutive three-component activation-alkynylation-cyclization reaction of (hetero)aryl glyoxylic acids, oxalyl chloride, arylacetylenes, and hydrazides efficiently forms 1,5-diacyl-5-hydroxypyrazolines in moderate to good yields. The structures were unambiguously corroborated by comprehensive NMR spectroscopy and X-ray structure analyses of selected derivatives.
- G?rgen, Christina,Boden, Katharina,Reiss, Guido J.,Frank, Walter,Müller, Thomas J.J.
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supporting information
p. 1360 - 1370
(2019/07/10)
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- Pd(OAc)2-Catalyzed Asymmetric Hydrogenation of α-Iminoesters
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An efficient Pd(OAc)2-catalyzed asymmetric hydrogenation of α-iminoesters was realized for the first time at 1 atm hydrogen pressure and room temperature. Pd(OAc)2, a less expensive Pd salt with low toxicity, was found to be the most suitable catalyst precursor rather than Pd(TFA)2 which is usually the catalyst of choice for homogeneous asymmetric hydrogenation. The chiral α-arylglycine fragments are widely found in many chiral products and bioactive molecules.
- Chen, Jianzhong,Li, Feilong,Wang, Fang,Hu, Yawen,Zhang, Zhenfeng,Zhao, Min,Zhang, Wanbin
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supporting information
p. 9060 - 9065
(2019/11/19)
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- UROLITHIN A AND DERIVATIVES THEREOF FOR USE IN THERAPY
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In some embodiments of the invention, inventive compounds (e.g., Formula (I), (IA), (II), and (III), and urolithin derivatives) are disclosed. Other embodiments include compositions (e.g., pharmaceutical compositions) comprising the inventive compound. Still other embodiments of the invention include compositions (e.g., pharmaceutical compositions) for treating, for example, certain diseases using the inventive compounds. Some embodiments include methods of using the inventive compound (e.g., in compositions or in pharmaceutical compositions) for administering and treating (e.g., diseases). Further embodiments include methods for making the inventive compounds. Additional embodiments of the invention are also discussed herein.
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Paragraph 00440
(2019/12/04)
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- Organocatalytic Nitroaldol Reaction Associated with Deuterium-Labeling
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A deuterium-labeling reaction of nitroalkanes in deuterium oxide and the subsequent nitroaldol reaction have been accomplished under basic and organocatalytic conditions to provide the deuterium-labeled β-nitroalcohols in high yields and high deuterium contents. β-Deuterated β-nitroalcohols could be smoothly obtained from the reaction of nitroalkanes and various electrophiles using the easily-removal basic resin WA30. Furthermore, the asymmetric nitroaldol reaction using nitromethane and α-keto esters as electrophiles in the presence of a quinine-derived organocatalyst in deuterium oxide could provide the desired β-deuterated nitroalcohol derivatives with high enantioselectivities. (Figure presented.).
- Yamada, Tsuyoshi,Kuwata, Marina,Takakura, Ryoya,Monguchi, Yasunari,Sajiki, Hironao,Sawama, Yoshinari
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supporting information
p. 637 - 641
(2017/12/13)
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- Pd-Catalyzed One-Pot Borylation/Intramolecular Asymmetric Arylation on α-Ketiminoamides: Innovative Approach to Chiral 3-Amino-2-oxindoles
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3-Amino-2-oxindole derivatives are a common framework found in many natural products and medicinal compounds and thus their synthesis is of significant importance. We report for the first time a one-pot approach for the synthesis of these compounds, using a bory-lation/intramolecular asymmetric arylation sequence starting from -ortho -bromo-α-ketimino amide derivatives. Pd(OAc) 2 was used as the pre-catalyst along with (R)-BINAP as the chiral source. We successfully obtained a family of 3-phenyl-3-(aryl-amino)-indolin-2-one derivatives (11 in total) with excellent yields (up to 98%) and enantioselectivities of up to 76% ee. The reaction is versatile and tolerant of a wide range of functional groups.
- Marques, Carolina S.,Lawrence, Simon E.,Burke, Anthony J.
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supporting information
p. 497 - 502
(2017/11/15)
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- Umpolung Reaction of α-Imino Thioesters and the Subsequent C-C Bond Formation with the Unexpected Alkylthio Rearrangement
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An umpolung reaction of the α-imino thioester was examined, and we found that α-imino thioesters were more effective substrates for the umpolung N-alkylation than conventional α-imino esters and they gave N-alkylated amino thioesters in high yields under mild reaction conditions in a short time. A new type of C-C bond formation followed by an unexpected rearrangement of the alkylthio group took place with the unsaturated ketones to afford the β-alkylthio-α-amino thioesters in high yields with good diastereoselectivity.
- Mizota, Isao,Ueda, Chihiro,Tesong, Yun,Tsujimoto, Yusuke,Shimizu, Makoto
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supporting information
p. 2291 - 2296
(2018/04/30)
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- Catalyst-free three-component synthesis of highly functionalized 2,3-dihydropyrroles
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An efficient synthesis of fully substituted 2,3-dihydropyrroles has been achieved in one step through the three-component reaction of amines, aromatic aldehydes and α-ketoamides. This atom-economical and catalyst-free reaction is highly stereoselective and generates underexplored heterocycles in a single step. These compounds were examined in an enzymatic assay that led to the identification of potent α-glucosidase inhibitors, thereby demonstrating the utility of this novel methodology in medicinal chemistry.
- Wang, Dong,Li, Linna,Feng, Hairong,Sun, Hua,Almeida-Veloso, Fabrice,Charavin, Marine,Yu, Peng,Désaubry, Laurent
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supporting information
p. 2775 - 2780
(2018/06/27)
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- Conjugate addition from the excited state
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Conjugate addition occurs efficiently from excited hydrazide based acrylanilides under both UV and metal free visible light irradiations. The reaction proceeds via an excited state encounter complex that bifurcates either via an electron or energy transfer pathway. The generality of excited state conjugate addition is demonstrated using chloromethylation and by thiol addition.
- Iyer, Akila,Ahuja, Sapna,Jockusch, Steffen,Ugrinov, Angel,Sivaguru, Jayaraman
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supporting information
p. 11021 - 11024
(2018/10/08)
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- E - Z isomerization in Suzuki cross-couplings of haloenones: Ligand effects and evidence for a separate catalytic cycle
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Suzuki cross-coupling of haloalkenes is generally assumed to occur with retention of the alkene stereochemistry. While studying Suzuki cross-couplings on E-1,2-dichlorovinyl phenyl ketone, we were surprised to observe extensive isomerization. More surprisingly, the ligand employed strongly influenced the degree of isomerization: DPEphos and Xantphos led to 96% isomerized cross-coupled product whereas reactions in the absence of a phosphine ligand, or reactions employing t-BuXantphos, gave 94% retention of stereochemistry. While E-Z isomerization in Pd-catalyzed vinylic couplings has previously been attributed to events within the cross-coupling catalytic cycle, we present experimental and computational evidence for a separate Pd-catalyzed isomerization process in these reactions.
- Chehal, Navneet K.,Budzelaar, Peter H. M.,Hultin, Philip G.
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supporting information
p. 1134 - 1143
(2018/02/22)
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- Novel synthesis of tetrahydro-1H-pyrrolo[1,2-a]imidazol-2-ones via decarboxylative cyclization reaction of α-amino acids and α-ketoamides
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An efficient and practical method was developed for the synthesis of tetrahydro-1H-pyrrolo[1,2-a]imidazol-2-ones based on the decarboxylative cyclization reaction of α-ketoamides and proline. In most cases, tetrahydro-1H-pyrrolo[1,2-a]imidazol-2-ones were obtained with perfect diastereoselectivity to give trans-isomer in excellent yield.
- Wu, Jia-shou,Jiang, Hua-jiang,Yang, Jian-guo,Jin, Zheng-neng,Chen, Ding-ben
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supporting information
p. 546 - 551
(2017/01/16)
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- PREPARATION OF MONOSACCHARIDES, DISACCHARIDES, TRISACCHARIDES, AND PENTASACCHARIDES OF HEPARINOIDS
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The present invention provides preparations of monosaccharides, disaccharides, trisaccharides, and pentasaccharides of heparinoids. The present invention also provides novel monosaccharides, disaccharides, trisaccharides and pentasaccharides for use in th
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Paragraph 0114; 0115
(2017/02/02)
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- N-Heterocyclic Carbene-Catalyzed Umpolung of Alkynyl 1,2-Diketones
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The umpolung of alkynyl 1,2-diketones via N-heterocyclic carbene (NHC) catalysis was achieved for the first time, allowing the rapid access to a large variety of synthetically and pharmaceutically important α-pyrones under very mild conditions. A completely new NHC-catalyzed umpolung pattern involving an O-acylated allenolate as the key intermediate was proposed. Moreover, an unprecedented reaction pathway, featured by a series of group migrations and new bond formation, was postulated to demonstrate the formation of the products. (Figure presented.).
- Kong, Xiangwen,Zhang, Guoxiang,Yang, Shuang,Liu, Xiaozhi,Fang, Xinqiang
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supporting information
p. 2729 - 2734
(2017/08/23)
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- A mild method for the replacement of a hydroxyl group by halogen. 1. Scope and chemoselectivity
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α-Chloro-, bromo- and iodoenamines, which are readily prepared from the corresponding isobutyramides have been found to be excellent reagents for the transformation of a wide variety of alcohols or carboxylic acids into the corresponding halides. Yields are high and conditions are very mild thus allowing for the presence of sensitive functional groups. The reagents can be easily tuned allowing therefore the selective monohalogenation of polyhydroxylated molecules. The scope and chemoselectivity of the reactions have been studied and reaction mechanisms have been proposed.
- Munyemana, Fran?ois,George, Isabelle,Devos, Alain,Colens, Alain,Badarau, Eduard,Frisque-Hesbain, Anne-Marie,Loudet, Aurore,Differding, Edmond,Damien, Jean-Marie,Rémion, Jeanine,Van Uytbergen, Jacqueline,Ghosez, Léon
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p. 420 - 430
(2015/12/31)
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- Potassium Phosphate-Catalyzed Chemoselective Reduction of α-Keto Amides: Route to Synthesize Passerini Adducts and 3-Phenyloxindoles
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A chemoselective reduction of α-keto amides to biologically important α-hydroxy amides (mandelamides) by polymethylhydrosiloxane (PMHS) using 5 mol% potassium phosphate (K3PO4) as catalyst has been developed. This transition metal-free protocol discloses excellent chemoselectivity for the ketone reduction of α-keto amides in the presence of other reducible functionalities like ketone, nitro, halides, nitrile and amide. Also, the chemoselectively reduced α-hydroxy amide has been derivatized to isocyanide-free Passerini adducts. The N-alkyl-α-hydroxy amides have been successfully converted to 3-phenyloxindole derivatives by treatment with methanesulfonyl cholride and triethylamine.
- Muthukumar, Alagesan,Mamillapalli, N. Chary,Sekar, Govindasamy
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p. 643 - 652
(2016/02/27)
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- Tandem Chemoselective 1,2-/1,4-Migration of the Thio Group in Keto Thioesters: An Efficient Approach to Substituted Butenolides
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We report herein an efficient and mechanistically unique tandem chemoselective 1,2-/1,4-migration of the thio group in keto thioesters that provides substituted butenolides in moderate to excellent yields. Thus, α-keto thioesters in the presence of stabilized phosphonate carbanions undergo tandem 1,2-sulfur migration; whereas 1,4-migration of the thio group has been achieved with the same thioesters after the treatment with Wittig reagents followed by BF3?OEt2-catalyzed tandem reaction. The crossover experiments and the isolation of intermediates reveal a stepwise mechanism for both of these transformations. (Figure presented.).
- Mal, Kanchan,Naskar, Sandip,Sen, Shovan Kumar,Natarajan, Ramalingam,Das, Indrajit
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supporting information
p. 3212 - 3230
(2016/10/20)
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- AMINOESTER DERIVATIVES
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The invention relates to novel compounds which are both phosphodiesterase 4 (PDE4) enzyme inhibitors and muscarinic M3 receptor antagonists, methods of preparing such compounds, compositions containing them and therapeutic use thereof.
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Page/Page column 59
(2016/11/21)
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- Alkyl halide-free heteroatom alkylation and epoxidation facilitated by a recyclable polymer-supported oxidant for the in-flow preparation of diazo compounds
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Highly reactive metal carbenes, generated from simple ketones via diazo compounds, including diazoamides and -phosphonates, using a recyclable reagent inflow, are transient but versatile electrophiles for heteroatom alkylation reactions and for epoxide formation. The method produces no organic waste, with the only byproducts being water, KI and nitrogen, without the attendant hazards of isolation of intermediate diazo compounds.
- Nicolle, Simon M.,Hayes, Christopher J.,Moody, Christopher J.
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supporting information
p. 4576 - 4579
(2015/03/18)
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- METHODS AND COMPOSITIONS FOR SELECTIVE AND TARGETED CANCER THERAPY
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Provided herein are methods and compositions for selective and targeted cancer therapy, in particular certain benzothiophenes, benzothiazoles, oxalamides, N-acyl ureas and chromones, and their use in selectively treating certain adenocarcinomas. In some embodiments, the selective toxicity of the compounds may be mediated through SCD1 and/or CYP450 such as CYP4F11.
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Page/Page column 264
(2015/03/28)
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- Asymmetric 1,2-Perfluoroalkyl Migration: Easy Access to Enantioenriched α-Hydroxy-α-perfluoroalkyl Esters
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This study has led to the development of a novel, highly efficient, 1,2-perfluoro-alkyl/-aryl migration process in reactions of hydrate of 1-perfluoro-alkyl/-aryl-1,2-diketones with alcohols, which are promoted by a Zn(II)/bisoxazoline and form α-perfluoro-alkyl/-aryl-substituted α-hydroxy esters. With (-)-8-phenylmenthol as the alcohol, the corresponding menthol esters are generated in high yields with excellent levels of diastereoselectivity. The mechanistic studies show that the benzilic ester-type rearrangement reaction takes place via an unusual 1,2-migration of electron-deficient trifluoromethyl group rather than the phenyl group. The overall process serves as a novel, efficient, and simple approach for the synthesis of highly enantioenriched, biologically relevant α-hydroxy-α-perfluoroalkyl carboxylic acid derivatives.
- Wang, Pan,Feng, Liang-Wen,Wang, Lijia,Li, Jun-Fang,Liao, Saihu,Tang, Yong
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supporting information
p. 4626 - 4629
(2015/04/27)
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- Rhodium(I)-Catalyzed Intermolecular Hydroacylation of α-Keto Amides and Isatins with Non-Chelating Aldehydes
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The application of the bidentate, electron-rich bisphosphine ligand, 1,3-bis(dicyclohexyl)phosphine-propane (dcpp), in rhodium(I)-catalyzed intermolecular ketone hydroacylation is herein described. Isatins and α-keto amides are shown to undergo hydroacylation with a variety of non-chelating linear and branched aliphatic aldehydes. Also reported is the synthesis of new bidentate chiral phosphine ligands, and their application in hydroacylation is discussed.
- Kou, Kevin G. M.,Longobardi, Lauren E.,Dong, Vy M.
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supporting information
p. 2233 - 2237
(2015/07/27)
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- Enantioselective Construction of 3-Hydroxypiperidine Scaffolds by Sequential Action of Light and Rhodium upon N-Allylglyoxylamides
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3-Hydroxypiperidine scaffolds were enantioselectively constructed in an atom-economical way by sequential action of light and rhodium upon N-allylglyoxylamides. In a formal sense, the allylic C-H bond was selectively cleaved and enantioselectively added a
- Ishida, Naoki,Ne?as, David,Masuda, Yusuke,Murakami, Masahiro
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supporting information
p. 7418 - 7421
(2015/06/30)
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- Organocatalytic Enantioselective Michael Reaction of Malononitrile with β,β-Disubstituted Nitroalkenes
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We have developed and optimized an enantioselective Michael reaction of malononitrile with β,β-disubstituted nitroalkenes. This reaction was catalyzed by a cinchona alkaloid derived thiourea catalyst, producing products of high yields (up to 98 %) and ste
- Chen, Shengwei,Lou, Qinxin,Ding, Yuyang,Zhang, Shasha,Hu, Wenhui,Zhao, Junling
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supporting information
p. 2437 - 2441
(2015/08/18)
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- Reductive cyclization of halo-ketones to form 3-hydroxy-2-oxindoles via palladium catalyzed hydrogenation: a hydrogen-mediated Grignard addition
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Abstract The reductive cyclization of N-oxoacyl ortho-bromoanilides to form 3-hydroxy-2-oxindoles under the conditions of palladium catalyzed hydrogenation is described. This work may be viewed as a prelude to intermolecular hydrogen-mediated Grignard-typ
- Shin, Inji,Ramgren, Stephen D.,Krische, Michael J.
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supporting information
p. 5776 - 5780
(2015/08/03)
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- Nucleophilic β-Carbon Activation of Propionic Acid as a 3-Carbon Synthon by Carbene Organocatalysis
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Direct β-carbon activation of propionic acid (C2H5CO2H) by carbene organocatalysis has been developed. This activation affords the smallest azolium homoenolate intermediate (without any substituent) as a 3-carbon nucleophi
- Jin, Zhichao,Jiang, Ke,Fu, Zhenqian,Torres, Jaume,Zheng, Pengcheng,Yang, Song,Song, Bao-An,Chi, Yonggui Robin
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supporting information
p. 9360 - 9363
(2015/06/30)
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- Hydroxoiridium/Chiral Diene Complexes as Effective Catalysts for Asymmetric Annulation of α-Oxo- and Iminocarboxamides with 1,3-Dienes
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The asymmetric [3+2] annulation of α-oxo- and α-iminocarboxamides with 1,3-dienes catalyzed by hydroxoiridium/chiral diene complexes was realized, giving high yields of the corresponding γ-lactams with high enantioselectivity. [3+2] annulation: The asymme
- Hatano, Miyuki,Nishimura, Takahiro
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supporting information
p. 10949 - 10952
(2015/09/15)
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- Amino Acid Salt Catalyzed Asymmetric Synthesis of 1,2-Diols with A Quaternary Carbon Center
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Enantioenriched 1,2-diols with a quaternary carbon center have great potential in the preparation of natural and biologically active compounds, but remain challenging synthetic targets which demand for both good diastereo- and enantioselectivity. As part
- Wu, Quanquan,Liu, Shulei,Wang, Fangyuan,Li, Qingqing,Cheng, Kangli,Li, Juan,Jiang, Jun
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supporting information
p. 2442 - 2446
(2015/10/19)
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- Asymmetric friedel-crafts alkylation of α-substituted β-nitroacrylates: Access to β2,2-amino acids bearing indolic all-carbon quaternary stereocenters
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A highly enantioselective Friedel-Crafts alkylation reaction of indoles with acyclic α-substituted β-nitroacrylates is developed under the catalysis of Ni(ClO4)2-bisoxazoline complex at 1 mol % catalyst loading, affording chiral indolic β-nitroesters bearing all-carbon quaternary stereocenters in excellent yields and ees of up to 97%. Transformation of one of the products to β2,2-amino ester and tetrahydro-β-carboline through nitro reduction and sequential Pictet-Spengler cyclization was exemplified.
- Weng, Jian-Quan,Deng, Qiao-Man,Wu, Liang,Xu, Kai,Wu, Hao,Liu, Ren-Rong,Gao, Jian-Rong,Jia, Yi-Xia
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supporting information
p. 776 - 779
(2014/03/21)
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- Cationic Ir/Me-BIPAM-catalyzed asymmetric intramolecular direct hydroarylation of α-ketoamides
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Asymmetric intramolecular direct hydroarylation of α-ketoamides gives various types of optically active 3-substituted 3-hydroxy-2-oxindoles in high yields with complete regioselectivity and high enantioselectivities (84-98 % ee). This is realized by the use of the cationic iridium complex [Ir(cod) 2](BArF4) and the chiral O-linked bidentate phosphoramidite (R,R)-Me-BIPAM. Carbon's got a brand new bond: Asymmetric intramolecular direct hydroarylation of α-ketoamides gives various optically active 3-substituted 3-hydroxy-2-oxindoles in high yields with complete regioselectivity and high enantioselectivities. This is realized by the use of an asymmetric cationic iridium complex formed in situ (see Scheme).
- Shirai, Tomohiko,Ito, Hajime,Yamamoto, Yasunori
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supporting information
p. 2658 - 2661
(2014/03/21)
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- Potassium N-iodo p-toluenesulfonamide (TsNIK, iodamine-T): A new reagent for the oxidation of hydrazones to diazo compounds
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A new reagent for the oxidation of hydrazones to diazo compounds is described. N-Iodo p-toluenesulfonamide (TsNIK, iodamine-T) allows the preparation of α-diazoesters, α-diazoamides, α-diazoketones and α-diazophosphonates in good yield and in high purity after a simple extractive work-up. α-Diazoesters were also obtained in high yield from the corresponding ketones through a one-pot process of hydrazone formation/oxidation. Diazo compounds: N-Iodo p-toluenesulfonamide (TsNIK, iodamine-T), readily prepared from p-toluenesulfonamide and iodine in aqueous KOH, is a new reagent for the oxidation of hydrazones to diazo compounds in good yields and high purity (see scheme).
- Nicolle, Simon M.,Moody, Christopher J.
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supporting information
p. 4420 - 4425
(2014/05/06)
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- Enantio- and chemoselective Br?nsted-acid/Mg(nBu) 2 catalysed reduction of α-keto esters with catecholborane
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The first enantio- and chemoselective Br?nsted-acid catalysed reduction of α-keto esters with catecholborane has been developed. The α-hydroxy esters were obtained under mild reaction conditions in virtually quantitative yields and excellent enantioselectivities. With slight modifications both enantiomers can be obtained without any loss of selectivity. This journal is the Partner Organisations 2014.
- Enders, Dieter,St?ckel, Bianca A.,Rembiak, Andreas
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supporting information
p. 4489 - 4491
(2014/04/17)
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- Solvatochromic fluorescent 2-substituted 3-ethynyl quinoxalines: Four-component synthesis, photophysical properties, and electronic structure
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2-Substituted 3-ethynylquinoxalines can be rapidly synthesized in generally excellent yields by a consecutive four-component synthesis starting from electron-rich π-nucleophiles, oxalyl chloride, terminal alkynes, and 1,2-diaminoarenes. The title compound
- Gers, Charlotte F.,Nordmann, Jan,Kumru, Ceyda,Frank, Walter,Müller, Thomas J. J.
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p. 3296 - 3310
(2014/05/06)
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- Organocatalytic asymmetric synthesis of functionalized 1,3,5- triarylpyrrolidin-2-ones via an aza-Michael/aldol domino reaction
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The organocatalytic asymmetric synthesis of functionalized 1,3,5-triarylpyrrolidin-2-ones bearing three contiguous stereocenters through an aza-Michael/aldol domino reaction of α-ketoamides with α,β-unsaturated aldehydes is described. The domino products
- Joie, Celine,Deckers, Kristina,Enders, Dieter
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p. 799 - 808
(2014/04/03)
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- A new class of tunable dendritic diphosphine ligands: Synthesis and applications in the Ru-catalyzed asymmetric hydrogenation of functionalized ketones
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A series of tunable G0-G3 dendritic 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) ligands was prepared by attaching polyaryl ether dendrons onto the four phenyl rings on the P atoms. Their ruthenium complexes were employed in the asymmetric hydrogenation of β-ketoesters, α-ketoesters, and α-ketoamides to reveal the effects of dendron size on the catalytic properties. The second- and third-generation catalysts exhibited excellent enantioselectivities, which are remarkably higher than those obtained from the small molecular catalysts and the first-generation catalyst. Molecular modeling indicates that the incorporation of bulky dendritic wedges can influence the steric environments around the metal center. In addition, the ruthenium catalyst bearing a second-generation dendritic ligand could be recycled and reused seven times without any obvious decrease in enantioselectivity.
- Ma, Baode,Miao, Tingting,Sun, Yihua,He, Yanmei,Liu, Ji,Feng, Yu,Chen, Hui,Fan, Qing-Hua
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supporting information
p. 9969 - 9978
(2014/08/18)
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- The photochemical synthesis of N-arylacetyl lactams
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The photochemical formation is described of N-arylacetyl lactams from the corresponding N-phenylglyoxylic acid derivatives of pyrrolidine and piperidine-2-carboxylic acids in an acetone:water mixture containing potassium carbonate. Evidence is presented f
- Jiang, Lei,Ma, Nan,Qiu, Jun,Zhang, Ronghua
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p. 143 - 145
(2013/07/05)
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- Intramolecular Paterno-Buechi reaction of atropisomeric α-oxoamides in solution and in the solid-state
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Atropisomeric α-oxoamides were synthesized and employed for intramolecular Paterno-Buechi reaction leading to very high enantio- and diastereoselectivity in the bicyclic oxetane photoproduct. A reversal of product selectivity was observed in solution and in the solid-state.
- Raghunathan, Ramya,Kumarasamy, Elango,Iyer, Akila,Ugrinov, Angel,Sivaguru
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supporting information
p. 8713 - 8715
(2013/09/23)
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