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Solvent responsive self-separation behaviour of Br?nsted acidic ionic liquid-polyoxometalate hybrid catalysts on H2O2 mediated oxidation of alcohols
Two solvent responsive self-separative ionic liquid-based POM hybrids [DEDSA]3[PW12O40] and [DEDSA]3[PMo12O40] were prepared by combination of diethyldisulphoammonium chloride [DEDSA]Cl with Keggin phosphotungstic acid and phosphomolybdic acid. Properties like water tolerance, high activity, high thermal stability and reusability in these POM hybrid compounds facilitate a new type of POM based catalysis used for oxidation of organic alcohols using hydrogen peroxide as oxidizing agent. Due to varied solubility of the hybrid with different solvents, the hybrid can effectively catalyze the oxidation reaction in homogenous condition and then can finally switch back to heterogenous system and convert as self-precipitating catalyst on addition of suitable solvent at the end of the reaction, which made the recovery and reuse of the hybrid very convenient. The catalysts are characterized via different analytical and spectroscopic tools like FT-IR, 1H NMR, 13C NMR, 31P NMR, TGA, UV–Visible, Powder XRD techniques, Raman etc. It was found that the prepared material was highly acidic, thermally stable in nature and was recycled up to 7 times without much loss of catalytic activity.
Kashyap, Niharika,Das, Sukanya,Borah, Ruli
(2021)
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N-Heterocyclic Iod(az)olium Salts – Potent Halogen-Bond Donors in Organocatalysis
This article describes the application of N-heterocyclic iod(az)olium salts (NHISs) as highly reactive organocatalysts. A variety of mono- and dicationic NHISs are described and utilized as potent XB-donors in halogen-bond catalysis. They were benchmarked in seven diverse test reactions in which the activation of carbon- and metal-chloride bonds as well as carbonyl and nitro groups was achieved. N-methylated dicationic NHISs rendered the highest reactivity in all investigated catalytic applications with reactivities even higher than all previously described monodentate XB-donors based on iodine(I) and (III) and the strong Lewis acid BF3.
Boelke, Andreas,Kuczmera, Thomas J.,Lork, Enno,Nachtsheim, Boris J.
supporting information
p. 13128 - 13134
(2021/08/09)

Modular access to 1,2-allenyl ketones based on a photoredox-catalysed radical-polar crossover process
Herein, a new protocol dealing with the preparation of 1,2-allenyl ketones has been successfully developedviathe reactions of enynes with radicals enabled by dual photoredox/copper catalysis. Based on the results of a deuteration experiment and the competition reaction between cyclopropanation and allenation, the mechanism based on a photoredox-neutral-catalysed radical-polar crossover process has been proposed. Synthetic applications of allenes have also been demonstrated.
Du, Chan,Fang, Jianghua,Fang, Yewen,Lei, Wan,Li, Yan,Liu, Yongjun
supporting information
p. 8502 - 8506
(2021/10/20)

Mild Darzens Annulations for the Assembly of Trifluoromethylthiolated (SCF3) Aziridine and Cyclopropane Structures
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.
supporting information
p. 6121 - 6125
(2021/08/16)

Photocatalytic Stoichiometric Oxidant-Free Synthesis of Linear Unsaturated Ketones from 1,2-Disubstituted Cyclopropanols
A one-step catalytic oxidant-free synthesis of unsaturated ketones from 1,2-disubstituted cyclopropanols is reported. Previously for this transformation, only two- and three-step protocols have been developed. The reaction proceeds under irradiation with visible light in the presence of catalytic amounts of both an acridinium photocatalyst and a cobaloxime complex. 2-Aryl-substituted cyclopropanols react giving α,β-unsaturated ketones, while dehydrogenative ring opening of 2-alkyl-substituted substrates affords mixtures of α,β- and β,γ-enones. The reaction starts with one-electron oxidation of a cyclopropanol to cyclopropyloxy radical, presumably, by the photoexcited acridinium catalyst. We also found that Co(dmgBF 2) 2(MeCN) 2complex under an air atmosphere and irradiation with blue LEDs or upon heating can serve as a hydroxycyclopropane oxidant.
Laktsevich-Iskryk, Marharyta V.,Krech, Anastasiya V.,Zhabinskii, Vladimir N.,Khripach, Vladimir A.,Hurski, Alaksiej L.
p. 1077 - 1086
(2020/12/14)

Method for preparing phenyl propenone compound by catalyzing phenylacetylene through molecular sieve
The invention belongs to the field of molecular sieve catalysis and organic synthesis, and discloses a method for preparing a phenyl propenone compound by catalyzing phenylacetylene through a molecular sieve, which comprises the following steps: adding a phenylacetylene compound I, aldehyde II and a molecular sieve catalyst into a small reaction kettle without adding an organic solvent and any other assistants; performing stirring to react for 0.25-6 hours under the condition of heating at 30-90 DEG C, cooling the reaction kettle to room temperature, performing diluting with ethyl acetate, andcentrifugally separating the catalyst to obtain the phenyl allyl ketone compound III. The molecular sieve catalyst provided by the invention is H-beta of which the silica-alumina ratios are respectively 14 and 29. The method is simple in reaction process, high in catalytic activity and selectivity, recyclable, environmentally friendly and capable of achieving large-scale industrial production.
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Paragraph 0040-0070

(2021/03/13)

Generation of α-Boryl Radicals and Their Conjugate Addition to Enones: Transition-Metal-Free Alkylation of gem-Diborylalkanes
A transition-metal-free method for the alkylation of gem-diborylalkanes with α,β-unsaturated ketones has been developed. It is demonstrated that the α-boryl radicals can be generated efficiently from gem-diborylalkanes with the aid of catechol and oxidants. The α-boryl radicals formed through such process can be engaged in conjugate addition reaction with α,β-unsaturated ketones. This transformation is a straightforward method for the synthesis of γ-borylketones.
Wu, Chaoqiang,Bao, Zhicheng,Dou, Bowen,Wang, Jianbo
supporting information
p. 2294 - 2298
(2021/01/18)

Diversified Transformations of Tetrahydroindolizines to Construct Chiral 3-Arylindolizines and Dicarbofunctionalized 1,5-Diketones
Enantioselective diverse synthesis of a small-molecule collection with structural and functional similarities or differences in an efficient manner is an appealing but formidable challenge. Asymmetric preparation and branching transformations of tetrahydroindolizines in succession present a useful approach to the construction of N-heterocycle-containing scaffolds with functional group, and stereochemical diversity. Herein, we report a breakthrough toward this end via an initial diastereo- A nd enantioselective [3 + 2] cycloaddition between pyridinium ylides and enones, following diversified sequential transformations. Chiral N,N′-dioxide-earth metal complexes enable the generation of optically active tetrahydroindolizines in situ, across the strong background reaction for racemate-formation. In connection with deliberate sequential transformations, involving convenient rearomatic oxidation, and light-active aza-Norrish II rearrangement, the tetrahydroindolizine intermediates were converted into the final library including 3-arylindolizine derivatives and dicarbofunctionalized 1,5-dicarbonyl compounds. More importantly, the stereochemistry of four-stereogenic centered tetrahydroindolizine intermediates could be efficiently transferred into axial chirality in 3-arylindolizines and vicinal pyridyl and aryl substituted 1,5-diketones. In addition, densely functionalized cyclopropanes and bridged cyclic compounds were also discovered depending on the nature of the pyridinium ylides. Mechanism studies were involved to explain the stereochemistry during the reaction processes.
Feng, Xiaoming,He, Qianwen,Liu, Xiaohua,Pan, Chenjing,Su, Zhishan,Wu, Zhikun,Zhang, Dong,Zhou, Yuqiao
supporting information
p. 15975 - 15985
(2020/10/18)

Photoredox/Cobalt Dual-Catalyzed Decarboxylative Elimination of Carboxylic Acids: Development and Mechanistic Insight
Recently, dual-catalytic strategies towards the decarboxylative elimination of carboxylic acids have gained attention. Our lab previously reported a photoredox/cobaloxime dual catalytic method that allows the synthesis of enamides and enecarbamates directly from N-acyl amino acids and avoids the use of any stoichiometric reagents. Further development, detailed herein, has improved upon this transformation's utility and further experimentation has provided new insights into the reaction mechanism. These new developments and insights are anticipated to aid in the expansion of photoredox/cobalt dual-catalytic systems.
Cartwright, Kaitie C.,Joseph, Ebbin,Comadoll, Chelsea G.,Tunge, Jon A.
p. 12454 - 12471
(2020/09/09)

Enantioselective N -Alkylation of Nitroindoles under Phase-Transfer Catalysis
An asymmetric phase-transfer-catalyzed N -alkylation of substituted indoles with various Michael acceptors was studied. Acidities of nitroindoles were determined in acetonitrile by UV-Vis spectrophotometric titration. There was essentially no correlation between acidity and reactivity in the aza-Michael reaction. The position of the nitro group on the indole ring was essential to control the stereoselectivity of the reaction. Michael adducts were obtained in high yields and moderate enantioselectivities in the reaction between 4-nitroindole and various Michael acceptors in the presence of cinchona alkaloid based phase-transfer catalysts. In addition to outlining the scope and limitations of the method, the geometries of the transition states of the reaction were calculated.
Erkman, Kristin,J?rving, Ivar,K?ster, Kristjan,Kanger, T?nis,Leito, Ivo,Mart?nova, Jevgenija,Metsala, Andrus,Saame, Jaan,Trubits?n, Dmitri
p. 1047 - 1059
(2020/04/01)

Electrochemical C(sp 3)-H Fluorination
A simple and robust method for electrochemical alkyl C-H fluorination is presented. Using a simple nitrate additive, a widely available fluorine source (Selectfluor), and carbon-based electrodes, a wide variety of activated and unactivated C-H bonds are converted into their C-F congeners. The scalability of the reaction is also demonstrated with a 100 gram preparation of fluorovaline.
Baran, Phil S.,Chen, Longrui,Chen, Miao,Hoshikawa, Tamaki,Kawamata, Yu,Li, Chao,Mykhailiuk, Pavel,Nakamura, Hugh,Peters, Byron K.,Reisberg, Solomon H.,Shibuguchi, Tomoyuki,Takahira, Yusuke
supporting information
p. 1178 - 1182
(2019/06/08)

Organocatalytic Enantioselective Selenosulfonylation of a C-C Double Bond to Form Two Stereogenic Centers in an Aqueous Medium
Organocatalytic selenosulfonylation of the C-C double bond of α,β-unsaturated ketones to construct two contiguous stereogenic centers in an aqueous medium was described. A series of α-selenyl and β-sulfonyl ketones with various functional groups were synthesized in good yields and enantioselectivities with saturated NaCl solution as the solvent. In addition, this protocol had been successfully scaled up to a decagram scale via a simple workup procedure.
Chen, Zhili,Hu, Fangli,Huang, Shengli,Zhao, Zhengxing,Mao, Hui,Qin, Wenling
p. 8100 - 8111
(2019/06/17)

Facile Synthesis of Onychines
The FeCl 3 -mediated condensation of an α-phenylenamino ester and an enone proceeds efficiently to afford a 2-phenylnicotinate. The subsequent intramolecular Friedel-Crafts reaction yielded an onychine framework. Modifications at the 2-, 3-, and 8-positions of the onychine framework were easily achieved by altering the enamino esters and enones, which facilitated the discovery of potentially bioactive compounds.
Arita, Mao,Yokoyama, Soichi,Asahara, Haruyasu,Nishiwaki, Nagatoshi
p. 2007 - 2013
(2019/04/26)

Activation of Michael Acceptors by Halogen-Bond Donors
Extending earlier studies on iodine catalysis, experimental investigations show that various halogen-bond donors can also be employed to accelerate the Michael addition between trans -crotonophenone and indole. Solvent as well as counteranion effects have been analyzed, and kinetic and computational investigations provide additional insights into the mode of activation.
Von Der Heiden, Daniel,Detmar, Eric,Kuchta, Robert,Breugst, Martin
supporting information
p. 1307 - 1313
(2017/12/08)

Indium(III)-Catalyzed Hydration and Hydroalkoxylation of α,β-Unsaturated Ketones in Aqueous Media
The hydration of α,β-unsaturated ketones with water proceeded efficiently in the presence of In(OTf)3 (20 mol%) in aqueous media to afford synthetically versatile β-hydroxyketones in moderate to good yields with good functional group compatibility. The method also can be extended to the hydroalkoxylation of α,β-unsaturated ketones with various alcohols for the efficient synthesis of β-alkoxyketones as well as tetrahydrofuran derivatives. (Figure presented.).
Yun, Jin-Jin,Zhi, Man-Ling,Shi, Wen-Xiao,Chu, Xue-Qiang,Shen, Zhi-Liang,Loh, Teck-Peng
supporting information
p. 2632 - 2637
(2018/05/30)

Chromium(III)-Catalyzed Addition of Water and Alcohol to α,β-Unsaturated Ketones for the Synthesis of β-Hydroxyl and β-Alkoxyl Ketones in Aqueous Media
An efficient chromium(III) chloride-catalyzed Michael-type reaction of water or alcohol with α,β-unsaturated ketones is developed. A variety of α,β-unsaturated ketones effectively reacted with either water or alcohols to give the corresponding β-hydroxyl ketones or β-alkoxyl ketones in modest to high yields with excellent compatibility to various functional groups. The approach was further utilized for the preparation of synthetically useful compounds containing tetrahydrofuran skeleton.
Yun, Jin-Jin,Liu, Xuan-Yu,Deng, Wei,Chu, Xue-Qiang,Shen, Zhi-Liang,Loh, Teck-Peng
p. 10898 - 10907
(2018/09/06)

Synthesis of Enones and Enals via Dehydrogenation of Saturated Ketones and Aldehydes
A general, efficient and economic palladium-catalyzed dehydrogenation to form enones or enals has been developed. The approach possesses extremely broad substrate scope including various linear or cyclic saturated ketones and aldehydes. The protocol is ligand-free, and molecular oxygen is used as the sole clean oxidant in the reaction. Due to mild reaction conditions, good functional group compatibility, and versatile utilities of enones and enals, the method can be applied in the late-stage synthesis of natural products, pharmaceuticals and fine chemicals. (Figure presented.).
Pan, Gao-Fei,Zhu, Xue-Qing,Guo, Rui-Li,Gao, Ya-Ru,Wang, Yong-Qiang
p. 4774 - 4783
(2018/11/10)

Solvent free, light induced 1,2-bromine shift reaction of α-bromo ketones
Photolysis of α-bromopropiophenones in acetonitrile results in formation of β-bromopropiophenones with good product selectivity, which can be coined as 1,2-Br shift reaction. The product selectivity increases when the reaction is done in neat or solid state, where only the 1,2-Br shift product is formed in some cases. The reaction is suggested to proceed by C–Br bond homolysis to give a radical pair, followed by disproportionation and conjugate addition of HBr to the α,β-unsaturated ketone intermediate. When the unsaturated intermediate is stabilized by an extra conjugation, the reaction stops at the stage, in which the unsaturated ketone becomes a major product. The synthetic method described in this research fits in a category of eco-friendly organic synthesis nicely since the reaction does not use volatile organic solvents and any other additives such as acid, base or metal catalysts, etc. Besides, the method fits into perfect atom economy, which does not give any side products. The synthetic method should find much advantage over other alternative methods to obtain β-bromo carbonyl compounds.
An, Sejin,Moon, Da Yoon,Park, Bong Ser
p. 6922 - 6928
(2018/10/24)

Synthesis of a Bolm's 2,2′-Bipyridine Ligand Analogue and Its Applications
A new method of synthesis of an analogue of Bolm's 2,2′-bipyridine ligand based on the catalytic [2+2+2] cyclotrimerization of 1-halodiynes with nitriles was developed. Crucial step of the whole synthesis turned out to be homodimerization of a substituted 2-bromopyridine to the corresponding bipyridine, that was studied and optimized. The newly prepared bipyridine (S,S)-2 was then tested as a chiral ligand in metal-catalyzed enantioselective reactions. Out of the studied reactions the most promising results were obtained in epoxide ring opening (82% yield, 98% ee) and Mukaiyama aldol reaction (>96% yield, 99/1 dr, 92% ee). In the case of Mukaiyama-aldol reaction as well as in the Michael addition, novel ligand 2 proved its robustness compared to Bolm's ligand as it was less sensitive to the purity of used reagents. (Figure presented.).
Bedná?ová, Eva,Dra?ínsky, Martin,Malatinec, ?tefan,Císa?ová, Ivana,Lamaty, Frédéric,Kotora, Martin
p. 2869 - 2878
(2018/08/17)

Environment-friendly method for synthesizing propenyl ketone compound
The invention discloses an environment-friendly method for synthesizing a propenyl ketone compound. The method comprises the following steps: subjecting an aldehyde compound and allyl bromide to a Barbier reaction in the presence of metal powder, so as to obtain an allyl alcohol compound; and subjecting the allyl alcohol compound to a structural isomerization reaction in the presence of a catalyst, thereby obtaining the propenyl ketone compound. The method disclosed by the invention has the advantages of short synthesis route, mild reaction conditions, simplicity in operation, readily available raw materials, and the like and has relatively high academic research value and market economy significance.
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Paragraph 0019; 0026

(2019/01/04)

Reaction Mechanism of Iodine-Catalyzed Michael Additions
Molecular iodine, an easy to handle solid, has been successfully employed as a catalyst in different organic transformations for more than 100 years. Despite being active even in very small amounts, the origin of this remarkable catalytic effect is still unknown. Both a halogen bond mechanism as well as hidden Br?nsted acid catalysis are frequently discussed as possible explanations. Our kinetic analyses reveal a reaction order of 1 in iodine, indicating that higher iodine species are not involved in the rate-limiting transition state. Our experimental investigations rule out hidden Br?nsted acid catalysis by partial decomposition of I2 to HI and suggest a halogen bond activation instead. Finally, molecular iodine turned out to be a similar if not superior catalyst for Michael additions compared with typical Lewis acids.
Von Der Heiden, Daniel,Bozkus, Seyma,Klussmann, Martin,Breugst, Martin
p. 4037 - 4043
(2017/04/28)

An iron-catalyzed hydroalkylation reaction of α,β-unsaturated ketones with ethers
A general strategy for the hydroalkylation of vinyl ketones using ethers catalyzed by an iron catalyst is described. This catalytic method permits direct transformation of easily accessible and abundant precursors into highly substituted, structurally diverse and functionally concentrated products.
Lan, Yun,Fan, Pei,Liu, Xiao-Wei,Meng, Fei-Fan,Ahmad, Tanveer,Xu, Yun-He,Loh, Teck-Peng
supporting information
p. 12353 - 12356
(2017/11/20)

Halogen-bonded iodonium ion catalysis: A route to α-hydroxy ketones: Via domino oxidations of secondary alcohols and aliphatic C-H bonds with high selectivity and control
A domino synthesis of α-hydroxy ketones has been developed from benzylic secondary alcohols employing catalytic iodonium ions stabilized by DMSO. The reaction proceeds through an unprecedented sequential oxidation of alcohols to ketone and its α-hydroxylation in a controlled manner. The spectroscopic evidence establishes the possibility of formation of a stable halogen-bonded adduct between DMSO and iodonium ions.
Guha, Somraj,Kazi, Imran,Mukherjee, Pranamita,Sekar, Govindasamy
supporting information
p. 10942 - 10945
(2017/10/13)

Copper-Catalyzed Carbenoid Insertion Reactions of α-Diazoesters and α-Diazoketones into Si-H and S-H Bonds
An efficient copper-catalyzed carbenoid insertion reaction of α-diazo carbonyl compounds into Si-H and S-H bonds was developed. A wide range of α-silylesters and α-thioesters was obtained in high yields (up to 98%) from α-diazoesters using 5 mol% of a simple copper(I) salt as catalyst. Using 0.05 mol% of the same catalyst, α-diazoketones led to α-silylketones in low to good yields (up to 70%).
Keipour, Hoda,Jalba, Angela,Delage-Laurin, Léo,Ollevier, Thierry
p. 3000 - 3010
(2017/03/23)

Bifunctional Thiourea-Catalyzed Stereoablative Retro-Sulfa-Michael Reaction: Concise and Diastereoselective Access to Chiral 2,4-Diarylthietanes
Owing to the chiral recognition capacity of bifunctional thioureas, a stereoablative retro-sulfa-Michael reaction has been developed. Utilization of a biphasic system enabled us to render the process catalytic. The usefulness of this methodology was further illustrated by the diastereoselective synthesis of all possible stereoisomers of 2,4-diarylthiethanes.
Bacsó, András,Szigeti, Mariann,Varga, Szilárd,Soós, Tibor
p. 429 - 439
(2016/12/24)

Palladium(II)-Catalyzed Dehydroboration via Generation of Boron Enolates
The PdII-catalyzed dehydroboration of boron enolates generated from ketones and 9-iodo-9-borabicyclo[3.3.1]nonane was achieved, providing a synthetically versatile protocol from ketones to α,β-unsaturated ketones. The PdIIcompound employed in this reaction worked catalytically in the presence of Cu(OAc)2. The high trans-selectivity of the olefinic moiety was observed. Aryl halide moieties (-Br and -Cl) remained intact for this reaction in spite of the presence of a Pd species. An ester substrate could also be applied when a stoichiometric amount of PdIIwas used. The crossover reactions using boron and silyl enolates revealed that the oxidation reaction is much faster than the Saegusa-Ito reaction.
Sakamoto, Yuki,Amaya, Toru,Suzuki, Takeyuki,Hirao, Toshikazu
p. 18686 - 18689
(2016/12/26)

Preparation, Antiepileptic Activity, and Cardiovascular Safety of Dihydropyrazoles as Brain-Penetrant T-Type Calcium Channel Blockers
A series of dihydropyrazole derivatives was developed as potent, selective, and brain-penetrating T-type calcium channel blockers. An optimized derivative, compound 6c, was advanced to in vivo studies, where it demonstrated efficacy in the WAG/Rij rat model of generalized nonconvulsive, absence-like epilepsy. Compound 6c was not efficacious in the basolateral amygdala kindling rat model of temporal lobe epilepsy, and it led to prolongation of the PR interval in ECG recordings in rodents.
Remen, Lubos,Bezen?on, Olivier,Simons, Lloyd,Gaston, Rick,Downing, Dennis,Gatfield, John,Roch, Catherine,Kessler, Melanie,Mosbacher, Johannes,Pfeifer, Thomas,Grisostomi, Corinna,Rey, Markus,Ertel, Eric A.,Moon, Richard
supporting information
p. 8398 - 8411
(2016/10/03)

A convenient synthesis of 4-alkyl-3-benzoylpyrroles from α,β-unsaturated ketones and tosylmethyl isocyanide
A convenient synthesis of 4-alkyl-3-benzoyl pyrrole was achieved from α,β-unsaturated ketones and tosylmethyl isocyanide in the presence of mild base LiOH·H2O. This method is very economical and was successfully utilized for the synthesis of various 4-alkyl-3-benzoylpyrrole derivatives with good to excellent yields.
Kumar, Kapil,More, Shital S.,Goyal, Sandeep,Gangar, Mukesh,Khatik, Gopal L.,Rawal, Ravindra K.,Nair, Vipin A.
p. 2315 - 2319
(2016/05/10)

Synthesis of Aromatic Retinoids and Curcuminoids and Evaluation of their Antiproliferative, Antiradical, and Anti-inflammatory Activities
Natural retinoids and curcuminoids are known for their broad spectrum of biological properties, such as antioxidant, anti-inflammatory, antitumor, and so forth. In this work, a convenient synthesis of aromatic retinoids and curcuminoids from vinyl or allyl ketones, and the corresponding alcohols, using olefin metathesis as a key reaction, was elaborated. The best yields and diastereoselectivities were obtained from allylic or homoallylic alcohols by employing the two-step cross-metathesis/oxidation procedure. The synthesized analogues were tested for their antiproliferative activity on human cancer cell lines of various origin (leukemia CEM, adenocarcinoma MCF7, cervical carcinoma HeLa) as well as for their antioxidant and anti-inflammatory activity in vitro. All examined derivatives exhibited strong anti-inflammatory activity in vitro without affecting cell viability. They also showed strong cytotoxicity against leukemia cell line CEM, except for 18 and 35. The antioxidant activity of the tested compounds was rather weak.
Morzycki, Jacek W.,Rárová, Lucie,Grúz, Ji?i,Sawczuk, Tomasz,Kie?czewska, Urszula,Siergiejczyk, Leszek,Wojtkielewicz, Agnieszka
p. 339 - 350
(2016/08/19)

Organocatalytic Enantioselective Vinylogous Aldol Reaction of Allyl Aryl Ketones to Activated Acyclic Ketones
The first catalytic asymmetric vinylogous aldol reaction of activated allyls to activated acyclic ketones is disclosed. A variety of activated acyclic ketones, such as trifluoromethyl ketones, α-ketoesters, and α-keto phosphonates, were found to be involved forming diverse γ-selective aldol adducts with high enantioselectivities (up to >99% ee). The method provides an effective, general strategy to access valuable chiral electron-withdrawing group-substituted tertiary hydroxyl-based carboxylic acids.
Jing, Zhenzhong,Bai, Xiangbin,Chen, Wenchao,Zhang, Gao,Zhu, Bo,Jiang, Zhiyong
p. 260 - 263
(2016/02/03)

2-Oxindole Acts as a Synthon of 2-Aminobenzoyl Anion in the K2CO3-Catalyzed Reaction with Enones: Preparation of 1,4-Diketones Bearing an Amino Group and Their Further Transformations
A convenient approach for the synthesis of 1,4-diketones bearing an amino group has been developed through the K2CO3-catalyzed reaction of 2-oxindoles with enones with the assistance of atmospheric O2 via sequential Michael addition-oxidation-ring-cleavage process. The further intramolecular reaction leads to the formation of benzoazepinone, quinoline, and 3-oxindole derivatives.
Miao, Chun-Bao,Zeng, Yu-Mei,Shi, Tong,Liu, Rui,Wei, Peng-Fei,Sun, Xiao-Qiang,Yang, Hai-Tao
p. 43 - 50
(2016/01/15)

Carbonylative coupling of allylic acetates with aryl boronic acids
The first allylic carbonylation reaction of allylic acetates with aryl boronic acids under carbon monoxide has been developed. Using Pd-PCy3 as a catalyst, a wide spectrum of allylic acetates was carbonylated in the presence of various aryl boronic acids, affording α,β-unsaturated aryl ketones in good to excellent yields. Preliminary studies indicate that carbon monoxide always inserts at the least substituted terminal allylic carbon and the resulting β,γ-unsaturated aryl ketones generally isomerise to the ketones obtained.
Ma, Wei,Xue, Dong,Yu, Ting,Wang, Chao,Xiao, Jianliang
supporting information
p. 8797 - 8800
(2015/05/20)

Oxa-Michael addition promoted by the aqueous sodium carbonate
An efficient Michael addition of alcohols to activated alkenes promoted by sodium carbonate with water as reaction medium has been developed. The reaction provides a general, economical and environmentally friendly approach for the synthesis of β-alkoxycarbonyl compounds.
Guo, Shi-Huan,Xing, Sheng-Zhu,Mao, Shuai,Gao, Ya-Ru,Chen, Wen-Liang,Wang, Yong-Qiang
supporting information
p. 6718 - 6720
(2014/12/11)

Trans-cis isomerization of vinylketones through triplet 1,2-biradicals
The irradiation of trans-vinylketones 1a-c yields the corresponding cis isomers 2a-c. Laser flash photolysis of 1a and 1b with 308 and 355 nm lasers results in their triplet ketones (T1K of 1), which rearrange to form triplet 1,2-biradicals 3a and 3b, respectively, whereas irradiation with a 266 nm laser produces their cis-isomers through singlet reactivity. Time-resolved IR spectroscopy of 1a with 266 nm irradiation confirmed that 2a is formed within the laser pulse. In comparison, laser flash photolysis of 1c with a 308 nm laser showed only the formation of 2c through singlet reactivity. At cryogenic temperatures, the irradiation of 1 also resulted in 2. DFT calculations were used to aid in the characterization of the excited states and biradicals involved in the cis-trans isomerization and to support the mechanism for the cis-trans isomerization on the triplet surface.
Ranaweera, R. A. A. Upul,Scott, Tianeka,Li, Qian,Rajam, Sridhar,Duncan, Alexander,Li, Rui,Evans, Anthony,Bohne, Cornelia,Toscano, John P.,Ault, Bruce S.,Gudmundsdottir, Anna D.
p. 10433 - 10447
(2015/03/14)

A mild isomerization reaction for β,γ-unsaturated ketone to α,β-unsaturated ketone
A series of β,γ-unsaturated ketones were isomerized to their corresponding α,β-unsaturated ketones by the introduction of DABCO in iPrOH at room temperature. The endo-cyclic double bond (β,γ-position) on ketone was rearranged to exo-cyclic double bond (α,β-position) under the reaction conditions.
Lee, Adam Shih-Yuan,Lin, Mei-Chun,Wang, Shu-Huei,Lin, Li-Shin
p. 371 - 376
(2015/02/05)

Palladium catalyzed cyclizations of oxime esters with 1,2-disubstituted alkenes: Synthesis of dihydropyrroles
Pd-catalyzed cyclizations of oxime esters with 1,2-dialkylated alkenes provide an entry to chiral dihydropyrroles. Substrate and catalyst controlled strategies for selective product formation (vs alternative pyrroles) are outlined.
Race, Nicholas J.,Bower, John F.
supporting information
p. 4616 - 4619
(2013/09/24)

Synthesis and properties of BF2-3,3′- dimethyldiarylazadipyrromethene near-infrared fluorophores
The first synthesis of both organic and aqueous soluble BF2 chelated 3,3′-dimethyl-5,5′-diarylazadipyrromethenes has been achieved. The fluorophores are emissive in organic and aqueous solvents with high quantum yields in the key biological near-infrared (NIR) spectral region of 675-700 nm. Following efficient cellular uptake from aqueous media the fluorophore can be readily visualized with confocal microscopy.
Wu, Dan,O'Shea, Donal F.
p. 3392 - 3395
(2013/07/26)

Synthesis of Z-alkenes from Rh(I)-catalyzed olefin isomerization of β,γ-unsaturated ketones
Developing olefin isomerization reactions to reach kinetically controlled Z-alkenes is challenging because formation of trans-alkenes is thermodynamically favored under the traditional catalytic conditions using acids, bases, or transition metals as the catalysts. A new synthesis of Z-alkenes from Rh(I)-catalyzed olefin isomerization of β,γ-unsaturated ketones to α,β-unsaturated ketones was developed, providing an easy and efficient way to access various Z-enones.
Zhuo, Lian-Gang,Yao, Zhong-Ke,Yu, Zhi-Xiang
p. 4634 - 4637
(2013/10/08)

Decarboxylative allylation of arylglyoxylic acids with allyl alcohol
A decarboxylative allylation of arylglyoxylic acids with allyl alcohol has been developed. In the presence of catalytic amounts of Pd(dba) 2 and PPh3, the substrates are in an esterification equilibrium with the allyl arylglyoxylates, which are continuously decarboxylated to give α,β-unsaturated ketones along with CO2 and water as the only byproducts.
Grünberg, Matthias F.,Goo?en, Lukas J.
p. 140 - 143
(2013/10/01)

Reactivities of mixed organozinc and mixed organocopper reagents: 9. Solvent dependence of group transfer selectivity in sp3C coupling and acylation of mixed diorganocuprates and diorganozincs
The selectivity and/or reactivity of organyl group transfer of mixed diorganocuprates in their alkyl coupling in THF depends on N- or O-donor solvents as cosolvents. Selective n-Bu group transfer is observed in room temperature alkylation of Grignard reagent derived stoichiometric n-BuPhCuMgBr reagent in THF:cosolvent and solvation effects do not change the group transfer ability. However, in the alkylation of catalytic mixed cuprates derived from CuI catalyzed n-BuPh2ZnMgBr and n-Bu2PhZnMgBr, group transfer ability depends on the solvation effect and it can be controlled by using N- or O-donor solvents. In alkylation of CuI catalyzed mixed zincate n-BuPh 2ZnMgBr and also n-Bu2PhZnMgBr in THF at reflux temperature Ph group transfer takes place (n-Bu/Ph transfer ratio is 1:9 and 4:6, respectively) whereas n-Bu transfer increases in THF:NMP (1:1) resulting n-Bu/Ph transfer ratio of 4:6 and 8:2, respectively. Group transfer ability in allylation of n-BuPhZn seems not to be solvent dependent. The solvent effect on the group transfer ability has been found to be dependent also on the R 1 and R2 partnership in room temperature benzoylation of catalytic mixed cuprates, R1R2CuZnI, derived from CuI catalyzed R1R2Zn. These results are briefly discussed in terms of solvation of mixed diorganocuprate and diorganozinc reagents and provide useful information in their atom-economic alkyl, allyl and acyl coupling reactions.
Erdik, Ender,Ero?lu, Fatma,Kalkan, Melike,Pekel, ?zgen ?mür,?zkan, Duygu,Serdar, Ebru Z.
p. 235 - 241
(2013/10/01)

Y(OTf)3 catalyzed substitution dependent oxidative C(sp 3)-C(sp3) cleavage and regioselective dehydration of β-allyl-β-hydroxydithioesters: Alternate route to α,β- unsaturated ketones and functionalized dienes
β-Allyl-β-hydroxydithioesters have been generated by the regioselective Grignard addition to the β-oxodithioesters. They have been successfully employed in selective C(sp3)-C(sp3) bond cleavage to construct α,β-unsaturated ketone res
Chowdhury, Sushobhan,Chanda, Tanmoy,Nandi, Ganesh Chandra,Koley, Suvajit,Janaki Ramulu,Pandey,Singh, Maya Shankar
p. 8899 - 8903
(2013/09/23)

Oxidative C-C bond cleavage of aldehydes via visible-light photoredox catalysis
The visible-light mediated oxidative C-C bond cleavage of aldehydes has been achieved in good yields at ambient temperature and open to air using Ru(bpy)3Cl2 (bpy = 2,2′-bipyridine) as the photoredox catalyst. Moreover, we further demonstrated the application in a tandem Michael/oxidative C-C bond cleavage reaction.
Sun, Hongnan,Yang, Chao,Gao, Fei,Li, Zhe,Xia, Wujiong
supporting information
p. 624 - 627
(2013/04/23)

Synthesis of β-sulfanyl ketones via a tandem rearrangement-conjugate addition reaction catalyzed by a Re(V)-oxo complex
A method for synthesizing β-sulfanyl ketones via a tandem rearrangement and conjugate addition reaction has been developed. This methodology provides access to a range of β-sulfanyl ketones through the rearrangement of propargyl alcohols to the corresponding enones followed by the conjugate addition of unactivated thiols. The one-pot, tandem transformation is catalyzed by ReOCl3(OPPh3)(S(CH3)2) affording aryl and alkyl β-sulfanyl ketones in good to excellent yield.
Garst, Alyson E.,Badiceanu, Alexandra D.,Nolin, Kristine A.
supporting information
p. 459 - 461
(2013/02/23)

Gold meets rhodium: Tandem one-pot synthesis of β-disubstituted ketones via meyer-schuster rearrangement and asymmetric 1,4-addition
An asymmetric one-pot tandem Au/Rh-catalyzed synthesis of highly enantioenriched β-disubstituted ketones starting from racemic propargyl alcohols is disclosed. The compatibility of the two metal complexes (Au/Rh) and their orthogonal ligand systems (NHC/d
Hansmann, Max M.,Hashmi, A. Stephen K.,Lautens, Mark
supporting information
p. 3226 - 3229
(2013/07/26)

One-Step Synthesis Method of 2,9-Dimethyl-4,7-Diphenyl-1,10- Phenanthroline
This invention, which belongs to the field of organic synthesis, involves “One-step synthetic method of 2,9-dimethyl-1,7-diphenyl-1,10-phenanthroline”. This method uses O-phenylenediamine and formula III to react under the condition of mixed-shrinking agent, the synthesis can be completed in one step, the stated mixed-shrinking agent is mixture of hydrochloric acid and organic acid. The organic acid serves as phase transfer catalyst and shrinking agent, meanwhile, as buffer reagent, organic acid reduces polymerization of III, and side products as well. The products gained are of high purity and the reaction is mild and easy to control. Since there is no polluting material added and generated, the waste is safe to discharge. In the after treatment of reaction, ketone solvent is used to reduce separation step and product lost, thus improving yield.
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(2012/07/13)

InCl3/Me3SiCl-catalyzed direct michael addition of enol acetates to α,β-unsaturated ketones
The direct Michael addition of enol acetates to α,β-unsaturated ketones was achieved using a combination of Lewis acid catalysts, InCl 3 and Me3SiCl, which furnished stable enol-form products that could be further transformed into functionalized 1,5-diketones by reactions with various electrophiles.
Onishi, Yoshiharu,Yoneda, Yuki,Nishimoto, Yoshihiro,Yasuda, Makoto,Baba, Akio
supporting information
p. 5788 - 5791
(2013/01/15)

Decarboxylative allylation of glyoxylic acids with diallyl carbonate
A catalyst system consisting of Pd(PPh3)4 and P(pTol)3 was found to effectively promote the intermolecular decarboxylative coupling of α-oxocarboxylic acids with diallyl carbonate to give α,β-unsaturated ketones. The key advantage of the new reaction protocol is that preformation of the allyl esters is not required. The reaction is believed to proceed via phosphane-mediated decarboxylation of the α-oxocarboxylates, leading to acyl anion equivalents that are allylated within the coordination sphere of the palladium catalyst. Under the reaction conditions, the double bond then migrates into conjugation with the carbonyl group. Copyright
Manjolinho, Filipe,Gruenberg, Matthias F.,Rodriguez, Nuria,Goossen, Lukas J.
supporting information; experimental part
p. 4680 - 4683
(2012/10/08)

PROTEIN CROSSLINKING INHIBITOR AND USE OF THE SAME
The present invention relates to: a ketone compound having transglutaminase-inhibiting activity, which is represented by the following Formula 1, 2, or 3: wherein R1 is a substituted or unsubstituted aryl or heterocyclyl group, R2, R3, and R4 are hydrogen atoms, n is 2, X is halogen, R5 and R6 independently represent a hydrogen atom or a substituted or unsubstituted C1-C10 alkyl, aryl, or aralkyl group, wherein R5 and R6 are not hydrogen atoms at the same time, or R5 and R6 may be taken together to form a saturated or unsaturated and substituted or unsubstituted heterocyclyl group containing a nitrogen atom (N); an inhibitor of protein crosslinking comprising the compound; and a composition for preventing or treating a protein-crosslinking causative disease, which comprises the compound or the protein crosslinking inhibitor.
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(2012/11/08)

Synthesis of α,β-unsaturated ketones by Pd-catalyzed decarboxylative allylation of α-oxocarboxylates
A palladium/p-tolylphosphine system has been developed that catalyzes the extrusion of carbon dioxide from α-oxocarboxylic acid allyl esters, leading to α,β-unsaturated ketones (see scheme). The palladium complex activates the substrate and mediates the carbon-carbon bond formation to give allyl ketones, and subsequent double bond shift to the α,β position. The actual decarboxylation step with formation of the acyl nucleophile is promoted by phosphine.
Rodriguez, Nuria,Manjolinho, Filipe,Gruenberg, Matthias F.,Goossen, Lukas J.
supporting information; experimental part
p. 13688 - 13691
(2012/01/15)

Structural study-guided development of versatile phase-transfer catalysts for asymmetric conjugate additions of cyanide
Unprecedented phase-transfer catalysts for the first example of an organocatalytic asymmetric conjugate addition of cyanide with acetone cyanohydrin are reported (see scheme). Utilizing an accessible cupreidinium salt and a cyanation reagent suitable for industrial scale, this reaction holds significant promise for practical asymmetric synthesis. The catalysts were developed as a result of key structural insights gained by X-ray analysis. Copyright
Provencher, Brian A.,Bartelson, Keith J.,Liu, Yan,Foxman, Bruce M.,Deng, Li
p. 10565 - 10569
(2011/12/05)