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Total Syntheses of Prenylated Isoflavones from Erythrina sacleuxii and Their Antibacterial Activity: 5-Deoxy-3′-prenylbiochanin A and Erysubin F
The prenylated isoflavones 5-deoxyprenylbiochanin A (7-hydroxy-4′-methoxy-3′-prenylisoflavone) and erysubin F (7,4′-dihydroxy-8,3′-diprenylisoflavone) were synthesized for the first time, starting from mono- or di-O-allylated chalcones, and the structure of 5-deoxy-3′-prenylbiochanin A was corroborated by single-crystal X-ray diffraction analysis. Flavanones are key intermediates in the synthesis. Their reaction with hypervalent iodine reagents affords isoflavones via a 2,3-oxidative rearrangement and the corresponding flavone isomers via 2,3-dehydrogenation. This enabled a synthesis of 7,4′-dihydroxy-8,3′-diprenylflavone, a non-natural regioisomer of erysubin F. Erysubin F (8), 7,4′-dihydroxy-8,3′-diprenylflavone (27), and 5-deoxy-3′-prenylbiochanin A (7) were tested against three bacterial strains and one fungal pathogen. All three compounds are inactive against Salmonella enterica subsp. enterica (NCTC 13349), Escherichia coli (ATCC 25922), and Candida albicans (ATCC 90028), with MIC values greater than 80.0 μM. The diprenylated natural product erysubin F (8) and its flavone isomer 7,4′-dihydroxy-8,3′-diprenylflavone (27) show in vitro activity against methicillin-resistant Staphylococcus aureus (MRSA, ATCC 43300) at MIC values of 15.4 and 20.5 μM, respectively. In contrast, the monoprenylated 5-deoxy-3′-prenylbiochanin A (7) is inactive against this MRSA strain.
Kwesiga, George,Kelling, Alexandra,Kersting, Sebastian,Sperlich, Eric,Von Nickisch-Rosenegk, Markus,Schmidt, Bernd
p. 3445 - 3453
(2020)
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Nickel Hydride Catalyzed Cleavage of Allyl Ethers Induced by Isomerization
This report discloses the deallylation of O - and N -allyl functional groups by using a combination of a Ni-H precatalyst and excess Bronsted acid. Key steps are the isomerization of the O - or N -allyl group through Ni-catalyzed double-bond migration followed by Bronsted acid induced O/N-C bond hydrolysis. A variety of functional groups are tolerated in this protocol, highlighting its synthetic value.
Kathe, Prasad M.,Berkefeld, Andreas,Fleischer, Ivana
supporting information
p. 1629 - 1632
(2021/02/09)

Reaction-based fluorescent silk probes with high sensitivity and selectivity to Hg2+and Ag+ions
The detection and removal of heavy metals in the environment is urgent and meaningful. In this work, two types of fluorescent functionalized silksOSPandASPhave been prepared using worm silk as the substrate. These fluorescent silk probes exhibit an obvious fluorescence quenching effect in the presence of Hg2+or Ag+, enabling silk to specifically detect Hg2+or Ag+. An obvious color response occurs under visible light, from yellow to brown or gray, thereby realizing dual-channel identification of fluorescence and colorimetry. In addition, its sensing mechanism has been studied, and it is found that the probe reacts with metal ions as a reactive response. Compared with the fluorescent probes bearing one C-C/C-C bond, the probes with two terminal C-C/C-C bonds are more sensitive. And the excellent recognition ability can make the limit of detection as low as 0.25 μM. This indicates that silk fluorescent probes can be used to detect Hg2+and/or Ag+
Cheng, Xinjian,Duan, Lian,Liu, Kaiqi,Xiao, Li
p. 4877 - 4887
(2021/04/21)

Allylphenols as a new class of human 15-lipoxygenase-1 inhibitors
In this study, a series of mono- and diallylphenol derivative were designed, synthesized, and evaluated as potential human 15-lipoxygenase-1 (15-hLOX-1) inhibitors. Radical scavenging potency of the synthetic allylphenol derivatives was assessed and the results were in accordance with lipoxygenase (LOX) inhibition potency. It was found that the electronic natures of allyl moiety and para substituents play the main role in radical scavenging activity and subsequently LOX inhibition potency of the synthetic inhibitors. Among the synthetic compounds, 2,6-diallyl-4-(hexyloxy)phenol (42) and 2,6-diallyl-4-aminophenol (47) showed the best results for LOX inhibition (IC50 = 0.88 and 0.80 μM, respectively).
Alavi, Seyed Jamal,Seyedi, Seyed Mohammad,Saberi, Satar,Safdari, Hadi,Eshghi, Hossein,Sadeghian, Hamid
p. 259 - 266
(2020/10/12)

Iodine-DMSO catalyzed chemoselective oxidative aromatization and deallylation, nondeallylation of aryl allyl ether of tetrahydro-β-carboline
We have developed a simple method for the chemoselective aromatization of tetrahydro-β-carboline with selective nondeallylation O-allyl groups in the presence of iodine (100 mol %) in dimethyl sulfoxide/H2O2. A convergent approach toward the oxidative aromatization with selective deallylation (deprotection) of O-allyl-tetrahydro-β-carboline using iodine in dimethyl sulfoxide/HCl has been described. The present protocol contains cheap catalyst, easy work up, normal reaction conditions, and high selectivity.
Gaikwad, Sunil V.,Gaikwad, Milind V.,Lokhande, Pradeep D.
supporting information
p. 1408 - 1414
(2021/04/26)

Controlled Reduction of Nitriles by Sodium Hydride and Zinc Chloride
A new protocol for the controlled reduction of nitriles to aldehydes was developed using a combination of sodium hydride and zinc chloride. The iminyl zinc intermediates derived from aromatic nitriles could be further functionalized with allylmetal nucleophiles to afford homoallylamines. As the method allows the reduction of various aliphatic and aromatic nitriles with a concise procedure under milder reaction conditions and exhibits wide functional group compatibility, it is well suited for use in various opportunities in chemical synthesis.
Chiba, Shunsuke,Ong, Derek Yiren
p. 1369 - 1378
(2020/04/27)

Ancillary ligands switch the activity of Ru–NHC-based oxidation precatalysts
Herein we demonstrate how the inner-sphere coordinating ligands switch the activity of Ru–NHC-based oxidation precatalysts in the oxidative conversion of olefins to carbonyl compounds, with the help of a series of systematically varied imidazolydene-NHC (Im-NHC) and triazolydene-NHC (Tz-NHC)-based ruthenium(II)-complexes. It is shown that the catalytic activity of the para-cymene-containing precatalysts varies in the order of [(Tz-NHC)Ru(para-cymene)Cl]+ > [(Im-NHC)Ru(para-cymene)Cl]+, while the order of activity of the MeCN-containing precatalysts is found to be reversed, i.e., [(Im-NHC)Ru(MeCN)4]2+ > [(Tz-NHC)Ru(MeCN)4]2+. Along with the electronic influence of the NHC ligands, the effect of the lability of the para-cymene and MeCN ligands, and the overall charge of the complexes might be attributed toward such a switching of catalytic activity. This finding led to develop a new precatalyst with improved activity which was further utilized in selective oxidation of a series of styrene substrates containing other oxidation-sensitive functionalities.
Gupta, Suraj K.,Mandal, Tanmoy,Gangber, Tejaswinee,Singh, Vivek,Choudhury, Joyanta
supporting information

(2019/10/28)

Introducing the Tishchenko reaction into sustainable polymer chemistry
Taking advantage of the structural characteristics of lignin-derived phenolic compounds, a combination of the Williamson and Tishchenko reactions produced a series of new α,ω-diene functionalized carboxylic ester monomers from both petrochemical and renewable resources, which were applicable in subsequent thiol-ene click and acyclic diene metathesis (ADMET) polymerizations, providing a series of poly(thioether esters) and unsaturated aromatic-aliphatic polyesters with high molecular weights.
Ren, Tianhua,Chen, Qin,Zhao, Changbo,Zheng, Qiang,Xie, Haibo,North, Michael
supporting information
p. 1542 - 1547
(2020/03/26)

Enantioselective Synthesis of 3-Fluorochromanes via Iodine(I)/Iodine(III) Catalysis
The chromane nucleus is common to a plenum of bioactive small molecules where it is frequently oxidized at position 3. Motivated by the importance of this position in conferring efficacy, and the prominence of bioisosterism in drug discovery, an iodine(I)/iodine(III) catalysis strategy to access enantioenriched 3-fluorochromanes is disclosed (up to 7:93 e.r.). In situ generation of ArIF2 enables the direct fluorocyclization of allyl phenyl ethers to generate novel scaffolds that manifest the stereoelectronic gauche effect. Mechanistic interrogation using deuterated probes confirms a stereospecific process consistent with a type IIinv pathway.
Daniliuc, Constantin G.,Gilmour, Ryan,Neufeld, Jessica,Sarie, Jér?me C.,Thiehoff, Christian
supporting information
p. 15069 - 15075
(2020/06/17)

Nitrile Synthesis by Aerobic Oxidation of Primary Amines and in situ Generated Imines from Aldehydes and Ammonium Salt with Grubbs Catalyst
Herein, a Grubbs-catalyzed route for the synthesis of nitriles via the aerobic oxidation of primary amines is reported. This reaction accommodates a variety of substrates, including simple primary amines, sterically hindered β,β-disubstituted amines, allylamine, benzylamines, and α-amino esters. Reaction compatibility with various functionalities is also noted, particularly with alkenes, alkynes, halogens, esters, silyl ethers, and free hydroxyl groups. The nitriles were also synthesized via the oxidation of imines generated from aldehydes and NH4OAc in situ. (Figure presented.).
Utsumi, Tatsuki,Noda, Kenta,Kawauchi, Daichi,Ueda, Hirofumi,Tokuyama, Hidetoshi
supporting information
p. 3583 - 3588
(2020/08/05)

LIGHT EMITTING APPARATUS AND ELECTRONIC DEVICE COMPRISING THE SAME
A light emitting apparatus affording high quality colors and energy economy and an electronic device comprising the light emitting apparatus.
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Paragraph 0103

(2020/11/24)

Nickel-catalyzed removal of alkene protecting group of phenols, alcohols via chain walking process
An efficient nickel-catalyzed removal of alkene protection group under mild condition with high functional group tolerance through chain walking process has been established. Not only phenolic ethers, but also alcoholic ethers can be tolerated with the retention of stereocenter adjacent to hydroxyl group. The new reaction brings the homoallyl group into a start of new type of protecting group.
Meng, Chenkai,Niu, Haolin,Ning, Juehan,Wu, Wengang,Yi, Jun
supporting information

(2020/02/04)

Coordination Booster-Catalyst Assembly: Remote Osmium Outperforming Ruthenium in Boosting Catalytic Activity
Presented herein is a set of bimetallic and trimetallic “coordination booster-catalyst” assemblies in which the coordination complexes [RuII(terpy)2] and [OsII(terpy)2] acted as boosters for enhancement of the catalytic activity of [RuII(NHC)(para-cymene)]-based catalytic site. The boosters accelerated the oxidative loss of para-cymene from the catalytic site to generate the active catalyst during the oxidation of alkenes and alkynes into corresponding aldehydes, ketones and diketones. It was found that the boosting efficiency of the [OsII(terpy)2] units was considerably higher than its congener [RuII(terpy)2] unit in these assemblies. Mechanistic studies were conducted to understand this unique improvement.
Mandal, Tanmoy,Singh, Vivek,Choudhury, Joyanta
supporting information
p. 4774 - 4779
(2019/11/11)

COMPOUNDS, SALTS THEREOF AND METHODS FOR TREATMENT OF DISEASES
The present disclosure relates to compounds according to Formula (I), useful for treating diseases.
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Paragraph 00420-00421

(2019/03/12)

COMPOUNDS, SALTS THEREOF AND METHODS FOR TREATMENT OF DISEASES
The present disclosure relates to compounds according to Formulae (I), (II) and (VIII), useful for treating diseases.
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Paragraph 00251; 00252

(2019/03/12)

Diester monomer containing carboxylic ester structure, polyester thereof and sulfur-containing polyester (by machine translation)
The invention discloses a diester monomer containing a carboxylic ester structure, a polyester thereof and a sulfur-containing polyester. The monomer is prepared from vanillin, butyraldehyde, p-hydroxybenzaldehyde, 3 - fluorine -4 - hydroxybenzaldehyde, 3 - bromo -4 - hydroxybenzaldehyde and 3 - methyl -4 - hydroxybenzaldehyde, and the reaction product is recrystallized or separated to obtain an enal monomer; 2) is reacted, with an enal monomer as a raw material, without a solvent or dissolved in an organic solvent. After the reaction product is recrystallized or separated from the chromatographic column, a dicarboxylic monomer containing a carboxylic acid ester structure is obtained. The polyester is prepared under the action of Hoveveveda-Grubrubbs catalyst and p-benzoquinone. The sulfur-containing polyester is prepared by reacting with a dithiol compound. The novel monomer and the polymer, provided by the invention, have the advantages of abundant raw material sources, simple preparation process, no generation of inflammable and explosive low boiling volatile matters, environmental protection, universality and the like. (by machine translation)
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Paragraph 0079-0083

(2019/10/01)

Photoredox-Coupled F-Nucleophilic Addition: Allylation of gem-Difluoroalkenes
A novel strategy for the expedient construction of CF3-embeded tertiary/quarternary carbon centers was developed by taking advantage of photoredox catalysis. Thanks to a key step of single-electron oxidation, electron-rich gem-difluoroalkenes, which otherwise are essentially reluctant towards F-nucleoplilic addition, now readily participate in this fluoroallylation reaction. Furthermore, this strategy provides an elegant example for the generation, as well as functionalization, of α-CF3-substituted benzylic radical intermediates using cheap and readily available starting materials.
Liu, Haidong,Ge, Liang,Wang, Ding-Xing,Chen, Nan,Feng, Chao
supporting information
p. 3918 - 3922
(2019/02/19)

Electrochemical 1,4-reduction of α,β-unsaturated ketones with methanol and ammonium chloride as hydrogen sources
A sustainable, chemoselective 1,4-reduction of α,β-unsaturated ketones by means of an electrochemical method is presented, wherein the extremely inexpensive ammonium chloride (NH4Cl) is applied as the only additive. The reaction proceeds smoothly in the air at ambient temperature. Mechanistic studies reveal that both NH4Cl and solvent methanol work as hydrogen donors.
Huang, Binbin,Li, Yanan,Yang, Chao,Xia, Wujiong
supporting information
p. 6731 - 6734
(2019/06/17)

Chemoselective oxidation and deprotection of para-methoxybenzylic position with (diacetoxyiodo)benzene in acetic-trifluoroacetic acid
(Diacetoxyiodo)benzene in the presence of acetic–trifluoroacetic acid in THF has been developed for the chemoselective para-methoxybenzylic C–H bond oxidation to provide aryl carbonyl compounds at room temperature. The reaction condition is also applicable for the chemoselective deprotection of para-methoxybenzyl (PMB) ether in the presence of benzyl ether.
Lin, Chun-Yu,Yang, Ping-Shin,Chou, Pang-Yu,Ong, Chi Wi
p. 365 - 367
(2018/01/01)

NH3?H2O: The Simplest Nitrogen-Containing Ligand for Selective Aerobic Alcohol Oxidation to Aldehydes or Nitriles in Neat Water
Aqueous ammonia (NH3?H2O) has been shown to serve as the simplest nitrogen-containing ligand to effectively promote copper-catalyzed selective alcohol oxidation under air in water. A series of alcohols with varying electronic and steric properties were selectively oxidized to aldehydes with up to 95 % yield. Notably, by increasing the amount of aqueous ammonia in neat water, the exclusive formation of aryl nitriles was also accomplished with good-to-excellent yields. Additionally, the catalytic system exhibits a high level of functional group tolerance with ?OH, ?NO2, esters, and heteroaryl groups all being amenable to the reaction conditions. This one-pot and green oxidation protocol provides an important synthetic route for the selective preparation of either aldehydes or nitriles from commercially available alcohols.
Zhang, Guofu,Ma, Danting,Zhao, Yiyong,Zhang, Guihua,Mei, Guangyao,Lyu, Jinghui,Ding, Chengrong,Shan, Shang
p. 885 - 889
(2018/12/10)

METHOD FOR PRODUCING CARBONYL COMPOUND
PROBLEM TO BE SOLVED: To provide a method for producing a carbonyl compound, allowing for improvement of ease of production and furthermore allowing for reduction of production cost, by positively utilizing inexpensive iodine. SOLUTION: A carbonyl compound is produced by mixing primary alcohol or secondary alcohol, and iodic acid (HIO3) in a non-solvent or an aprotic polar solvent based on the following general formula (1), where R1 is an optionally substituted linear- or branched 1-12C aliphatic group, or an optionally substituted aromatic group; R2 is a hydrogen atom, an optionally substituted linear- or branched 1-12C alkyl group, or an optionally substituted aromatic group; R1 and R2 each may be coupled with each other to form a ring of aromatic group or a non-aromatic group. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0032-0035; 0037-0040

(2018/03/23)

Umpolung of Carbonyl Groups as Alkyl Organometallic Reagent Surrogates for Palladium-Catalyzed Allylic Alkylation
Palladium-catalyzed allylic alkylation of nonstabilized carbon nucleophiles is difficult and remains a major challenge. Reported here is a highly chemo- and regioselective direct palladium-catalyzed C-allylation of hydrazones, generated from carbonyls, as a source of umpolung unstabilized alkyl carbanions and surrogates of alkyl organometallic reagents. Contrary to classical allylation techniques, this umpolung reaction utilizes hydrazones prepared not only from aryl aldehydes but also from alkyl aldehydes and ketones as renewable feedstocks. This strategy complements the palladium-catalyzed coupling of unstabilized nucleophiles with allylic electrophiles by providing an efficient and selective catalytic alternative to the traditional use of highly reactive alkyl organometallic reagents.
Zhu, Dianhu,Lv, Leiyang,Li, Chen-Chen,Ung, Sosthene,Gao, Jian,Li, Chao-Jun
supporting information
p. 16520 - 16524
(2018/11/23)

Electronically Mismatched Cycloaddition Reactions via First-Row Transition Metal, Iron(III)-Polypyridyl Complex
The iron(III)-polypyridyl complex and its derivatives showed sufficient oxidizing potential to act as a one-electron oxidant, producing radical cations from olefins and promoting the efficient radical cation [2 + 2] and [2 + 4] cycloaddition reactions. Subsequent chain propagation afforded trisubstituted cyclobutane or cyclohexene derivatives, and this facile route enables the replacement of rare metals with sustainable, green, and inexpensive iron in radical cation cycloadditions.
Shin, Jung Ha,Seong, Eun Young,Mun, Hyeon Jin,Jang, Yu Jeong,Kang, Eun Joo
supporting information
p. 5872 - 5876
(2018/09/25)

Synthesis and Evaluation of O 2-Derived Diazeniumdiolates Activatable via Bioorthogonal Chemistry Reactions in Living Cells
A class of O2-alkyl derived diazeniumdiolates 3a-f and 4a-c were designed and synthesized as new bioorthogonal NO precursors, which can be effectively uncaged in the presence of a palladium catalyst via bioorthogonal bond cleavage reactions to generate NO in living cancer cells, eliciting potent antiproliferative activity.
Lv, Tian,Wu, Jianbing,Kang, Fenghua,Wang, Tingting,Wan, Boheng,Lu, Jin-Jian,Zhang, Yihua,Huang, Zhangjian
supporting information
p. 2164 - 2167
(2018/04/30)

Carbonylative Coupling of Alkyl Zinc Reagents with Benzyl Bromides Catalyzed by a Nickel/NN2 Pincer Ligand Complex
An efficient catalytic protocol for the three-component assembly of benzyl bromides, carbon monoxide, and alkyl zinc reagents to give benzyl alkyl ketones is described, and represents the first nickel-catalyzed carbonylative coupling of two sp3-carbon fragments. The method, which relies on the application of nickel complexed with an NN2-type pincer ligand and a controlled release of CO gas from a solid precursor, works well with a range of benzylic bromides. Mechanistic studies suggest the intermediacy of carbon-centered radicals.
Andersen, Thomas L.,Donslund, Aske S.,Neumann, Karoline T.,Skrydstrup, Troels
supporting information
p. 800 - 804
(2017/12/26)

A Gold Carbene Manifold to Prepare Fused γ-Lactams by Oxidative Cyclisation of Ynamides
Gold-catalysed oxidative cyclisation reactions of ynamides offer great promise in γ-lactam synthesis but are limited by preferential over-oxidation to form α-keto imides. Evaluating the factors that might limit N-cyclisation pathways led to effective gold-catalysed conditions that allow access to different fused γ-lactams on changing the ynamide N-substituent and accommodate previously incompatible substitution patterns. New and efficient methods for the synthesis of functionalised 3-aryl indoles and cyclohepta[c]pyrrol-1-one derivatives are presented. These conditions illustrate the complementarity of gold catalysis to other metals.
Sánchez-Cantalejo, Fernando,Priest, Joshua D.,Davies, Paul W.
supporting information
p. 17215 - 17219
(2018/11/10)

Method for preparing aldehyde by oxidizing primary alcohol
The invention discloses a method for preparing aldehyde by catalytic oxidation of primary alcohol. The method comprises the steps that the primary alcohol as shown in a formula (I) or (III) is taken as a raw material, copper salt is taken as a catalyst, air is taken as an oxidizing agent, TEMPO (2,2,6,6-tetramethyl-1-piperidine-N-oxyl compound) is taken as a pro-oxygenic agent, ammonium hydroxide is taken as a co-catalyst and solvent, the primary alcohol, the copper salt, the air, the TEMPO and the ammonium hydroxide are mixed uniformly and react for 9 to 24 hours at the temperature of 60 to 120 DEG C; after the reaction, reaction liquid is subjected to aftertreatment to obtain aldehyde as shown in a formula (II) or (IV). The method has the advantages of high reaction rate and yield, low cost, convenience in operation and safety in reaction. The whole process is environmental friendly and free of pollution.
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Paragraph 0026; 0027; 0028; 0029; 0030; 0076; 0077-0080

(2017/07/21)

Polarity-Reversed Allylations of Aldehydes, Ketones, and Imines Enabled by Hantzsch Ester in Photoredox Catalysis
The polarity reversal (umpolung) reaction is an invaluable tool for reversing the chemical reactivity of carbonyl and iminyl groups, which subsequent cross-coupling reactions to form C?C bonds offers a unique perspective in synthetic planning and implementation. Reported herein is the first visible-light-induced polarity-reversed allylation and intermolecular Michael addition reaction of aldehydes, ketones, and imines. This chemoselective reaction has broad substrate scope and the engagement of alkyl imines is reported for the first time. The mechanistic investigations indicate the formation of ketyl (or α-aminoalkyl) radicals from single-electron reduction, where the Hantzsch ester is crucial as the electron/proton donor and the activator.
Qi, Li,Chen, Yiyun
supporting information
p. 13312 - 13315
(2016/10/30)

Method for preparing aldehyde/ketone by catalyzing alcohol oxidation with ferric salt
The invention provides a method for preparing aldehyde/ketone by catalyzing alcohol oxidation with a ferric salt. The method comprises the following steps: mixing a compound shown in a formula (I) of a substrate, a ferric salt catalyst, a cocatalyst TEMPO (tetramethylpiperidinooxy), an amino acid ligand and a solvent; carrying out return flow agitation in an oxygen or air atmosphere for 1 to 60 h; then post-processing a reaction solution to obtain a product, namely a compound shown in a formula (II). According to the method provided by the invention, the ferric acid which is low in cost, easily available and environment-friendly is used as the catalyst; amino acids which are rich in resource, low in cost, easily available and easy to modify in a natural field are used as the ligand; the reaction substrate is high in applicability; first-grade benzyl alcohol, second-grade benzyl alcohol, allyl alcohol, heterocyclic aromatic alcohols and the like can be converted into corresponding aldehyde/ketone at high yield by adopting an oxidation system of the invention.
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Paragraph 0038; 0039; 0040; 0091; 0092; 0093; 0094; 0995

(2016/10/07)

Synthetic utility of iodic acid in the oxidation of benzylic alcohols to aromatic aldehydes and ketones
Various primary and secondary benzylic alcohols were efficiently oxidized to aromatic aldehydes and aromatic ketones with iodic acid in DMF at 60?°C for 2?h and with iodic acid in the presence of TEMPO (5?mol?%) in DMF at room temperature, respectively. The former method was effective for the oxidation of sterically hindered alcohols at 60?°C and the latter method was effective for the oxidation of less sterically hindered alcohols at room temperature.
Imai, Sho,Togo, Hideo
p. 6948 - 6954
(2016/10/13)

Dramatic Effect of Ancillary NHC Ligand in the Highly Selective Catalytic Oxidative Carbon-Carbon Multiple Bond Cleavage
Selective and controlled oxidation of olefins to aldehydes is a commonly used important transformation in chemistry. However, chemists still use the dangerous and inconvenient ozonolysis method or the less selective, low-yielding Lemieux-Johnson protocol. In a program of developing effective catalysts for this important reaction, we disclose here that an ancillary ligand can play a dramatic role in the above catalytic phenomenon, depending on the design of the ligand precursor chosen. Proof-of-principle is demonstrated with the help of two newly designed [LnRuII-NHC] precatalysts (NHC = an imidazolydene-based NHC, Im-NHC, or a triazolydene-based NHC, Trz-NHC; Ln = para-cymene) for catalytic selective oxidation of olefins/alkynes to carbonyl compounds. With the electron-deficient Trz-NHC ligand, [(para-cymene)RuII(Im-Trz)]+ precatalyst was found to be an order of magnitude more efficient than the [(para-cymene)RuII(Im-NHC)]+ precatalyst.
Gupta, Suraj K.,Sahoo, Sandeep K.,Choudhury, Joyanta
supporting information
p. 2462 - 2466
(2016/08/16)

Synthesis and pharmacological properties of naturally occurring prenylated and pyranochalcones as potent anti-inflammatory agents
An efficient approach has been developed for the synthesis of naturally occurring prenylated chalcones viz. kanzonol C (1), stipulin (2), crotaorixin (3), medicagenin (4), licoagrochalcone A (5) and abyssinone D (6) along with the pyranochalcones paratocarpin C (7), anthyllisone (8) and 3-O-methylabyssinone A (9). The key step of the synthesis is a Claisen-Schmidt condensation. Subsequently, their anti-inflammatory effects were investigated in lipopolysaccharides (LPSs)-induced RAW-264.7 macrophages. Of the synthesized chalcones, compounds 5 (IC50 = 10.41 μmol/L), 6 (IC50 = 9.65 μmol/L) and 8 (IC50 = 15.34 μmol/L) show remarkable activity with no cytotoxicity. Compound 9 (IC50 = 4.5 μmol/L) exhibits maximum (83.6%) nitric oxide (NO) inhibition, but shows slight cytotoxicity. The results reveal that the chalcones bearing the prenyl group at 3- and/or 5-position on ring A (acetophenone moiety), i.e., 1-4 and 7 show weak, or no inhibition activity, whereas chalcones having the prenyl group only on ring B (aldehyde part), i.e., 5, 6 and 8 show significant activity on the production of inflammatory mediated NO with no cytotoxicity.
Damodar, Kongara,Kim, Jin-Kyung,Jun, Jong-Gab
supporting information
p. 698 - 702
(2016/05/19)

A Monooxygenase from Boreostereum vibrans Catalyzes Oxidative Decarboxylation in a Divergent Vibralactone Biosynthesis Pathway
The oxidative decarboxylation of prenyl 4-hydroxybenzoate to prenylhydroquinone has been frequently proposed for the biosynthesis of prenylated (hydro)quinone derivates (sometimes meroterpenoids), yet no corresponding genes or enzymes have so far been reported. A FAD-binding monooxygenase (VibMO1) was identified that converts prenyl 4-hydroxybenzoate into prenylhydroquinone and is likely involved in the biosynthesis of vibralactones and other meroterpenoids in the basidiomycete Boreostereum vibrans. Feeding of 3-allyl-4-hydroxybenzylalcohol, an analogue of the vibralactone pathway intermediate 3-prenyl-4-hydroxybenzylalcohol, generated 20 analogues with different scaffolds. This demonstrated divergent pathways to skeletally distinct compounds initiating from a single precursor, thus providing the first insight into a novel biosynthetic pathway for 3-substituted γ-butyrolactones from a shikimate origin.
Yang, Yan-Long,Zhou, Hui,Du, Gang,Feng, Ke-Na,Feng, Tao,Fu, Xiao-Li,Liu, Ji-Kai,Zeng, Ying
supporting information
p. 5463 - 5466
(2016/05/09)

Synthesis and biological evaluation of allylated mono-carbonyl analogues of curcumin (MACs) as anti-cancer agents for cholangiocarcinoma
A series of new allylated mono-carbonyl curcumin analogues (MACs) were designed and synthesized. In vitro cytotoxic activities of allylated MACs 6a–h together with previously reported analogues 4a–i and 7a–e, were tested against human cholangiocarcinoma cell lines including HUCCA, QBC-939 and RBE. Of all the compounds tested, 6c exhibited potent in vitro antiproliferative activity against the three tested cancer cell lines with IC50values of 8.7, 9.3 and 8.9 μM, respectively. Cell cycle analysis showed that 6c inhibited cell proliferation due to G2/M arrest. Furthermore, mechanistic studies revealed that 6c dose-dependently increased the level of Bax and inhibited the expression of Bcl-2, to induce cancer cell apoptosis. Taken together, this work provides a novel series of anti-cancer candidates for the treatment of cholangiocarcinoma.
Qiu, Chenyu,Hu, Yan,Wu, Ke,Yang, Ke,Wang, Nan,Ma, Yue,Zhu, Heping,Zhang, Yi,Zhou, Yunfang,Chen, Chao,Li, Shanshan,Fu, Lili,Zhang, Xiuhua,Liu, Zhiguo
supporting information
p. 5971 - 5976
(2016/12/09)

Synthesis and optimization of novel allylated mono-carbonyl analogs of curcumin (MACs) act as potent anti-inflammatory agents against LPS-induced acute lung injury (ALI) in rats
A series of novel symmetric and asymmetric allylated mono-carbonyl analogs of curcumin (MACs) were synthesized using an appropriate synthetic route and evaluated experimentally thru the LPS-induced expression of TNF-α and IL-6. Most of the obtained compounds exhibited improved water solubility as a hydrochloride salt compared to lead molecule 8f. The most active compound 7a was effective in reducing the Wet/Dry ratio in the lungs and protein concentration in bronchoalveolar lavage fluid. Meanwhile, 7a also inhibited mRNA expression of several inflammatory cytokines, including TNF-α, IL-6, IL-1β, and VCAM-1, in Beas-2B cells after Lipopolysaccharide (LPS) challenge. These results suggest that 7a could be therapeutically beneficial for use as an anti-inflammatory agent in the clinical treatment of acute lung injury (ALI).
Zhu, Heping,Xu, Tingting,Qiu, Chenyu,Wu, Beibei,Zhang, Yali,Chen, Lingfeng,Xia, Qinqin,Li, Chenglong,Zhou, Bin,Liu, Zhiguo,Liang, Guang
p. 181 - 193
(2016/06/09)

Mono-carbonyl curcumin analogue containing piperidone structure and application
The invention discloses a mono-carbonyl curcumin analogue containing a piperidone structure and application. The structure of the mono-carbonyl curcumin analogue is shown in the formula (I) or the formula (II); in the formula (I), R1 can be alkyl groups, naphthenic bases, benzyl groups, aroyl groups, substituent aroyl groups and sulfonyl groups optionally substituted by different substituent groups; in the formula (II), R2 can be piperazinyl, morpholinyl, pyrrolidyl and N, N-di-substituted alkyl optionally substituted by different substituent groups. A large amount of experimental study is performed on the technical field of mono-carbonyl curcumin analogues with substituent piperidone as a parent nucleus structure, a large amount of design, synthesis and pharmacological activity screening are performed on the mono-carbonyl curcumin analogues with substituent piperidone as the parent nucleus structure, one kind of single-carbonyl curcumin analogues with substituent piperidone as the parent nucleus structure are obtained, and the mono-carbonyl curcumin analogue containing the piperidone structure has the efficient and broad-spectrum anti-inflammatory application. Please see the formulae in the description.
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Paragraph 0050; 0054

(2017/02/09)

Application of substituted mono carbonyl curcumin compound containing allyl in preparing antitumor drug
The invention discloses application of a substituted mono carbonyl curcumin compound containing allyl in preparing antitumor drug. The mono carbonyl curcumin compound has a structure shown in a formula (I) or a pharmaceutically acceptable salt thereof, wherein A represents C, S, or O -NR1, R1 is independently selected from one or more of H, C1-C5 alkyl, phenyl benzene and benzyl group, n is 0 or 1, R is independently selected from one or more of H, hydroxyl, C1-C4, alkoxyl, pyrrolidine, morpholinyl and methyl N-piperazine. Test results show that the mono carbonyl curcumin compound has good stability and antitumor activity, and can be used as a potential antitumor drug.
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Paragraph 0090; 0091

(2017/05/02)

INHIBITORS OF THE NOTCH TRANSCRIPTIONAL ACTIVATION COMPLEX AND METHODS FOR USE OF THE SAME
Disclosed herein are inhibitors of the Notch transcriptional activation complex, and methods for their use in treating or preventing diseases, such as cancer. The inhibitors described herein can include compounds of Formula (I) and pharmaceutically acceptable salts thereof: Formula (I), wherein the substituents are as described.
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Paragraph 00118

(2016/10/11)

Symmetrical mono-carbonyl curcumin analog 6b, preparation method and applications thereof
The invention relates to a micromolecular compound, which contains an allyl substituent and takes 1,4-diene-3-one as the nucleus, a preparation method and applications thereof. The provided symmetrical mono-carbonyl curcumin analog 6b has a good stability. In the cell level, the compound 6b has a very good antitumor activity, especially for human bile duct cancer, has a good development prospect, and can be used as an anticancer micromolecular lead compound in clinic.
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Paragraph 0013; 0022; 0023

(2017/01/17)

Fluorous bispidine: A bifunctional reagent for copper-catalyzed oxidation and knoevenagel condensation reactions in water
Fluorous bispidine-type ligands have been developed to facilitate its recovery and reusability and to demonstrate its bifunctional property as a ligand and base in copper-catalyzed aerobic oxidation, the Knoevenagel condensation and tandem oxidation/Knoevenagel condensation in water under mild conditions. Application of the fluorous ligand was also extended to the surfactant-free copper-catalyzed allylic and benzylic sp3 C-H oxidation reaction in water. The fluorous ligands could be recovered using F-SPE with recovery ranging from 91-97% and could be reused five times with little loss of activity.
Ang, Wei Jie,Chng, Yong Sheng,Lam, Yulin
p. 81415 - 81428
(2015/10/06)

Organoselenium-catalyzed mild dehydration of aldoximes: An unexpected practical method for organonitrile synthesis
Areneselenenic acids (ArSeOH), readily generated from diaryl diselenides and H2O2 by in situ oxidation, were found to be effective and reusable catalysts for dehydration of aldoximes, leading to a practical and scalable preparation of useful organonitriles under mild conditions.
Yu, Lei,Li, Hongyan,Zhang, Xu,Ye, Jianqing,Liu, Jianping,Xu, Qing,Lautens, Mark
supporting information
p. 1346 - 1349
(2014/04/03)

Oxidation of alcohols to aldehydes or ketones with 1-acetoxy-1,2- benziodoxole-3(1H)-one derivatives
Various benzylic and aliphatic alcohols were smoothly oxidized to the corresponding aromatic aldehydes and ketones as well as aliphatic ketones by treatment with 1-acetoxy-5-nitro-1,2-benziodoxole-3(1H)-one (ANBX), 1-acetoxy-5-bromo-1,2-benziodoxole-3(1H)-one (ABBX), 1-acetoxy-5-chloro-1,2- benziodoxole-3(1H)-one (ACBX), and 1-acetoxy-5-fluoro-1,2-benziodoxole-3(1H)-one (AFBX). These new tri-valent iodine compounds were prepared from 5-substituted 2-iodobenzoic acids and meta-chloroperoxybenzoic acid (m-CPBA). ANBX and ABBX were the most effective reagents for this oxidation of alcohols, and this present reaction is very attractive because of the ease of product isolation and the reusability of the reagents.
Iinuma, Masataka,Moriyama, Katsuhiko,Togo, Hideo
p. 772 - 780
(2014/03/21)

Oxidation of Alcohols to Aldehydes or Ketones with 1-Acetoxy-1,2-benziodoxole-3(1H)-one Derivatives
Various benzylic and aliphatic alcohols were smoothly oxidized to the corresponding aromatic aldehydes and ketones as well as aliphatic ketones by treatment with 1-acetoxy-5-nitro-1,2-benziodoxole-3(1H)-one (ANBX), 1-acetoxy-5-bromo-1,2-benziodoxole-3(1H)-one (ABBX), 1-acetoxy-5-chloro-1,2-benziodoxole-3(1H)-one (ACBX), and 1-acetoxy-5-fluoro-1,2-benziodoxole-3(1H)-one (AFBX). These new trivalent iodine compounds were prepared from 5-substituted 2-iodobenzoic acids and meta-chloroperoxybenzoic acid (m-CPBA). ANBX and ABBX were the most effective reagents for this oxidation of alcohols, and this present reaction is very attractive because of the ease of product isolation and the reusability of the reagents.
Iinuma, Masataka,Moriyama, Katsuhiko,Togo, Hideo
p. 772 - 780
(2015/10/05)

An efficient palladium-catalyzed synthesis of cinnamyl ethers from aromatic halides, phenols, and allylic chloride
A one-pot, two-step catalytic protocol for the preparation of cinnamyl ethers from simple and readily available aryl halides, phenols and allyl chloride is reported for the first time. This simple and highly efficient palladium nanoparticles catalytic system shows good regio- and stereoselectivities and affords the desired products in good to high yields (49-85%) from aryl iodides. Furthermore, less reactive aryl bromides can also give the cinnamyl ethers in moderate yields (24-72%).
Wang, Wei,Zhou, Rong,Jiang, Zhi-Jie,Wang, Kun,Fu, Hai-Yan,Zheng, Xue-Li,Chen, Hua,Li, Rui-Xiang
supporting information
p. 616 - 622
(2014/05/20)

Synthesis and biological evaluation of allylated and prenylated mono-carbonyl analogs of curcumin as anti-inflammatory agents
Curcumin has been shown to possess anti-inflammatory activities but has been limited for its low stability and poor bioavailability. We have previously reported four series of 5-carbon linker-containing mono-carbonyl analogs of curcumin (MACs). In continuation of our ongoing research, we designed and synthesized 33 novel allylated or prenylated MACs here, and evaluated their anti-inflammatory effects in RAW 264.7 macrophages. A majority of them effectively inhibited the LPS-induced expression of TNF-α and IL-6, especially IL-6. The preliminary SAR and quantitative SAR analysis were conducted. Compound 14q is the most potent analog among them, and exhibits significant protection against LPS-induced death in septic mice. Together, these data present a series of new analogs of curcumin as promising anti-inflammatory agents.
Liu, Zhiguo,Tang, Longguang,Zou, Peng,Zhang, Yali,Wang, Zhe,Fang, Qilu,Jiang, Lili,Chen, Gaozhi,Xu, Zheng,Zhang, Huajie,Liang, Guang
p. 671 - 682
(2014/03/21)

Design, economical synthesis and antiplasmodial evaluation of vanillin derived allylated chalcones and their marked synergism with artemisinin against chloroquine resistant strains of Plasmodium falciparum
The in vitro blood stage antiplasmodial activity of a series of allylated chalcones based on the licochalcone A as lead molecule was investigated against chloroquine (CQ) sensitive Pf3D7 and CQ resistant PfINDO strains of Plasmodium falciparum using SYBR Green I assay. Of the forty two chalcones tested, eight showed IC50 ≥ 5 μM. Structure-activity relationship (SAR) studies revealed 9 {1-(4-Chlorophenyl)-3-[3-methoxy-4-(prop-2-en-1-yloxy)phenyl] -prop-2-en-1-one} as the most potent (IC∑: 2.5 μM) against Pf3D7 with resistance indices of 1.2 and 6.6 against PfDd2 and PfINDO strains, respectively. Later on, the synergistic effects 9 with standard antimalarials {artemisinin (ART) and chloroquine (CQ)} were studied in order to provide the basis for the selection of the best partner drug. In vitro combinations of 9 with ART showed strong synergy against PfINDO (ΣFIC∑: 0.31-0.72) but additive to slight antagonistic effects (ΣFIC∑: 1.97-2.64) against Pf3D7. ΣFIC∑ 0.31 of ART+9 combination corresponded to a 320 fold and 3 fold reduction in IC∑ of 9 and ART, respectively. Similar combinations of 9 with CQ showed synergy to additivity to mild antagonism against the two strains {ΣFIC∑: 0.668-2.269 (PfINDO); 1.45-2.83 (Pf3D7)}. Drug exposure followed by drug withdrawal indicated that 9 taken alone at IC∑ killed rings, trophozoites and schizonts of P. falciparum. The combination of ART and 9 (1X ΣFIC∑) selectively inhibited the growth of rings while the 2X ΣFIC∑ combination of the same caused killing of rings without affecting trophozoites and schizonts. In contrast, the 1X combination of CQ and 9 (ΣFIC ∑: 0.5) killed rings and trophozoites. DNA fragmentation and loss of mitochondrial membrane potential (ΔΨm) in the 9 treated P. falciparum culture indicated apoptotic death in malaria parasites. Prediction of ADME properties revealed that most of the molecules did not violate Lipinski's parameters and have low TPSA value suggesting good absorption. The results suggest the promising drug-like properties of 9 against CQ resistant Pf and propensity for synergy with classical antimalarial drugs together with easy and economical synthesis.
Sharma, Nandini,Mohanakrishnan, Dinesh,Sharma, Upendra Kumar,Kumar, Rajesh,Richa,Sinha, Arun Kumar,Sahal, Dinkar
p. 350 - 368
(2014/05/06)

Stannous chloride dihydrate-mediated efficient access to secondary and primary amides from oximes
Highly selective, efficient and expeditious Beckmann rearrangement of a wide range of ketoximes to secondary amides (20 examples) has been accomplished using stoichiometric amount of stannous chloride dihydrate in the presence of nucleophilic additive, tetra-n-butylammonium iodide (TBAI) (10 moI%) and 4 ? MS in dry acetonitrile at reflux temperature. Aldoximes delivered primary amides through intermediacy of nitriles upon heating with an equimolar amount of SnCl2·2H2O and DBU in dry toluene at reflux in good to acceptable yields (12 examples). Utilization of mild Lewis acid, inexpensive rack reagents and procedural simplicity including easy isolation of products are key advantageous features of the protocol.
Ganguly, Nemai C.,Nayek, Subhasis,Chandra, Sumanta
p. 1695 - 1702
(2014/01/17)

Facile oxidation of alcohols to aldehydes or ketones with 1-acetoxy-5-nitro-1,2-benziodoxole-3(1 H)-one
Various benzylic alcohols and aliphatic secondary alcohols were smoothly oxidized to the corresponding aromatic aldehydes, aromatic ketones, and aliphatic ketones, respectively, with the novel 1-acetoxy-5-nitro-1,2- benziodoxole-3(1H)-one (ANBX) alone, a trivalent iodine prepared from the oxidation of 2-iodo-5-nitrobenzoic acid with MCPBA. The present reaction is the first effective method for the oxidation of alcohols with a trivalent iodine alone under mild reaction conditions. Georg Thieme Verlag Stuttgart New York.
Iinuma, Masataka,Moriyama, Katsuhiko,Togo, Hideo
p. 1707 - 1711
(2013/09/02)

Expanding the regioselective enzymatic repertoire: Oxidative mono-cleavage of dialkenes catalyzed by Trametes hirsuta
The first report of a biocatalytic regioselective oxidative mono-cleavage of dialkenes was successfully achieved employing a cell-free enzyme preparation from Trametes hirsuta at the expense of molecular oxygen. Selected reactions were performed on a preparative scale affording high to excellent conversions and chemoselectivities. The Royal Society of Chemistry 2012.
Paul, Caroline E.,Rajagopalan, Aashrita,Lavandera, Ivan,Gotor-Fernandez, Vicente,Kroutil, Wolfgang,Gotor, Vicente
supporting information; experimental part
p. 3303 - 3305
(2012/04/23)

Synthesis of 1-indanonyl oxepanes
A variety of 1-indanonyl oxepanes with the novel structure of indanonyl oxepanes was prepared from reaction of hydroxybenzaldehydes via a series of reasonable transformations, including the regioselective PhBClmediated allylation (or Claisen rearrangement), one-pot reaction of ring-closing metathesis and the Wittig olefination, hydrogenation, and the Friedel-Crafts intramolecular cyclization. Georg Thieme Verlag Stuttgart . New York.
Chang, Meng-Yang,Lee, Nien-Chia
scheme or table
p. 867 - 872
(2012/06/01)