- Multistep Synthesis and Nematicidal Activity of 2-(8-azabicyclo[3.2.1]octan-3-yl)-3-imino-2,3-dihydro-1H-isoindol-1-One Derivatives
-
[Figure not available: see fulltext.] Novel 2-(8-azabicyclo[3.2.1]octan-3-yl)-3-imino-2,3-dihydro-1H-isoindol-1-ones derived from 5-HT3 receptor antagonists hexahydroazepinylbenzamides were designed and synthesized through isocyanide insertion reaction. All target compounds were evaluated against pinewood nematodes B. xylophilus and root-knot nematodes M. incognita. Good lethal rate (75%) for 3-(tert-butylimino)-5-chloro-2-(8-methyl-8-azabicyclo[3.2.1]octan-3-yl)-2,3-dihydro-1H-isoindol-1-one and serious nervous curl effect against pinewood nematodes B. xylophilus for 3-(tert-butylimino)-2-(8-methyl-8-azabicyclo[3.2.1]octan-3-yl)-2,3-dihydro-1H-isoindol-1-one were observed at 10 mg/l. The inhibition activities of 3-[(4-methoxyphenyl)imino]-2-(8-methyl-8-azabicyclo[3.2.1]octan-3-yl)-2,3-dihydro-1H-isoindol-1-one against root-knot nematodes M. incognita were 84% at 160 mg/l and 60% at 20 mg/l for in vitro test and test tube test, respectively.
- Xu, Jun,Yang, Tianjiao,Wang, Jiayi,Song, Gonghua
-
-
- Phenanthridine Derivative Host Heat Shock Cognate 70 Down-Regulators as Porcine Epidemic Diarrhea Virus Inhibitors
-
Porcine epidemic diarrhea virus (PEDV) has become increasingly problematic around the world, not only for its hazards to livestock but also due to the possibility that it is a zoonotic disease. Although vaccine therapy has made some progress toward PEDV c
- Chen, Duo-Zhi,Fan, Shi-Rui,Yang, Bi-Juan,Yao, Huo-Chun,Wang, Yi-Ting,Cai, Jie-Yun,Jing, Chen-Xu,Pan, Zi-Hao,Luo, Miao,Yuze, Yan-Qiu,Liu, Guang-Jin,Hao, Xiao-Jiang
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p. 1175 - 1184
(2021/05/05)
-
- Synthesis of Methoxy-, Methylenedioxy-, Hydroxy-, and Halo-Substituted Benzophenanthridinone Derivatives as DNA Topoisomerase IB (TOP1) and Tyrosyl-DNA Phosphodiesterase 1 (TDP1) Inhibitors and Their Biological Activity for Drug-Resistant Cancer
-
As a recently discovered DNA repair enzyme, tyrosyl-DNA phosphodiesterase 1 (TDP1) removes topoisomerase IB (TOP1)-mediated DNA protein cross-links. Inhibiting TDP1 can potentiate the cytotoxicity of TOP1 inhibitors and overcome cancer cell resistance to
- Hu, De-Xuan,Tang, Wen-Lin,Zhang, Yu,Yang, Hao,Wang, Wenjie,Agama, Keli,Pommier, Yves,An, Lin-Kun
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p. 7617 - 7629
(2021/06/25)
-
- Ni-Catalyzed Reductive Arylcyanation of Alkenes
-
We disclose a Ni-catalyzed reductive arylcyanation of alkene using environmentally benign and nontoxic organo cyanating reagent N-cyano-N-phenyl-p-toluenesulfonamide. This reaction provides a new method for the rapid synthesis of cyano-substituted oxindoles and isoquinoline-1,3-diones and features high functional group tolerance. In addition, an enantioselective version was developed for the construction of enantiomerically enriched 3-cyanomethyl oxindole. This method has also been applied to the synthesis of natural alkaloids (+)-esermethole and (+)-physostigmine.
- Li, Hengxu,Chen, Jiachang,Dong, Jueqi,Kong, Wangqing
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supporting information
p. 6466 - 6470
(2021/08/23)
-
- Direct Synthesis of Enamides via Electrophilic Activation of Amides
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A novel, one-step N-dehydrogenation of amides to enamides is reported. This reaction employs the unlikely combination of LiHMDS and triflic anhydride, which serves as both the electrophilic activator and the oxidant, and is characterized by its simple setup and broad substrate scope. The synthetic utility of the formed enamides was readily demonstrated in a range of downstream transformations.
- Berger, Martin,Kaiser, Daniel,Maulide, Nuno,Spie?, Philipp
-
supporting information
p. 10524 - 10529
(2021/07/28)
-
- Modification of 5-methylphenanthridium from benzothiazoles to indoles as potent FtsZ inhibitors: Broadening the antibacterial spectrum toward vancomycin-resistant enterococci
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The death caused by pathogenic bacteria has always been a severe threat to mankind. The prevalence of drug resistance among bacteria underscores an urgent goal for new antibacterial agents with novel mode of action. Here we first designed and synthesized a class of benzothiazolyl-5-methylphenanthridium derivatives and evaluated their antibacterial activity. On this basis, we further designed and synthesized another class of novel indolyl-5-methylphenanthridium derivatives by optimizing the benzothiazolyl-5-methylphenanthridium core and evaluated their antibacterial activity targeting the bacterial cell division protein FtsZ. The results showed that the indolyl-5-methylphenanthridium derivatives had greatly improved activity against various drug-resistant bacterial strains including methicillin-resistant Staphylococcus aureus and vancomycin-resistant Enterococcus (VRE). Among them, compound C5 displayed excellent antibacterial activity against susceptible (MIC = 1 μg/mL), methicillin-resistant and clinical isolated S. aureus (MIC = 2 μg/mL). With low hemolytic activity towards mice red blood cells, C5 exhibited good antibacterial effect in vivo in preliminary pharmacodynamic assay. More importantly, C5 was difficult to induce bacterial resistance. Further mechanism studies proved that C5 could inhibit bacterial cell division by promoting FtsZ polymerization, leading to disorderly polymerization and disordered knots. Therefore, our findings suggest that this class of novel indolyl-5-methylphenanthridium derivatives are promising for future antibacterial agents.
- Chen, Weijin,Ma, Shutao,Song, Di,Zhang, Na,Zhang, Nan,Zhang, Panpan,Zhang, Shenyan
-
-
- Stereoinvertive C–C Bond Formation at the Boron-Bound Stereogenic Centers through Copper-Bipyridine-Catalyzed Intramolecular Coupling of α-Aminobenzylboronic Esters
-
Enantiospecific intramolecular Suzuki–Miyaura-type coupling with α-(2-halobenzoylamino)benzylboronic esters to give 3-substituted isoindolinones is achieved by using copper catalysts with 2,2′-bipyridine-based achiral ligands. Enantioenriched α-aminobenzylboron reactants bearing a hydrogen atom at the boron-bound stereogenic carbons undergo stereoinvertive coupling in the presence of a 6-phenyl-2,2′-bipyridine ligand with high enantiospecificity. α-Aminobenzylboronates bearing fully substituted boron-bound stereogenic centers also gave the 3,3-disubstituted isoindolinones with stereospecific stereochemical inversion in the presence of simple 2,2′-bipyridine as a ligand.
- Suginome, Michinori,Yamamoto, Takeshi,Yoshinaga, Yukako
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supporting information
p. 7251 - 7255
(2020/03/23)
-
- Enantiotropic Transformation of Carbethoxyhydrazones of Acetophenones
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Abstract: Hydrazinecarboxylates have been synthesized by reacting substituted acetophenones with carbethoxyhydrazine. One of product is formed as a mixture of E- and Z-isomers. In the process of measuring the melting point of the resulting hydrazinecarbox
- Bessonov, V. V.,Nepochatyi, G. D.,Petrov, M. L.,Pevzner, L. M.,Popova, E. A.,Stepanova, O. V.
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p. 311 - 313
(2020/04/15)
-
- Isoquinolinone derivatives as potent CNS multi-receptor D2/5-HT1A/5-HT2A/5-HT6/5-HT7 agents: Synthesis and pharmacological evaluation
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In this study, a series of novel Isoquinolinone derivatives were synthesized as potential multi-target antipsychotics. Among these, compound 13 showed high affinity for dopamine D2 and serotonin 5-HT1A, 5-HT2A, 5-HT6, and 5-HT7 receptors, showed low affinity for off-target receptors (5-HT2C, H1, and α1), and negligible effects on ether-a-gogo-related gene (hERG; i.e., reduced QT interval prolongation). An animal behavioral study revealed that compound 13 reversed APO-induced hyperlocomotion, MK-801-induced hyperactivity, and DOI-induced head twitch. Moreover, compound 13 exhibited a high threshold for acute toxicity, a lack of tendency to induce catalepsy, and did not cause prolactin secretion or weight gain when compared to risperidone. Furthermore, in the forced swim test, tail suspension test, and novel object recognition test, treatment with compound 13 resulted in improvements in depression and cognitive impairment. In addition, compound 13 had a favorable pharmacokinetic profile in rats. Thus, the antipsychotic drug-like effects of compound 13 indicate that it may be useful for developing a novel class of drugs for the treatment of schizophrenia.
- Cao, Xudong,Chen, Yin,Dou, Fei,Gao, Lanchang,Hao, Chao,Jin, Jian,Liu, Bi-Feng,Liu, Xin,Xiong, Jiaying,Zhang, Guisen,Zhang, Kunxiao,Zhang, Yifang
-
-
- Cobalt-Catalyzed Regio- A nd Enantioselective Allylic Alkylation of Malononitriles
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Cobalt-catalyzed highly branched- A nd enantioselective allylic alkylation of malononitriles has been developed. Chiral ?,?′-unsaturated malononitriles could be synthesized with >20:1 branched/linear regioselectivity and up to 99% enantiomeric excess from easily accessible racemic allylic carbonates under mild reaction conditions. The electron-rich and sterically less hindered bisoxazolinephosphine ligand is essential to realize the high reactivity in the carbon-carbon bond formation process.
- Ghorai, Samir,Ur Rehman, Sajid,Xu, Wen-Bin,Huang, Wen-Yu,Li, Changkun
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supporting information
p. 3519 - 3523
(2020/05/05)
-
- Palladium-Catalyzed Stereoselective Aza-Wacker-Heck Cyclization: One-Pot Stepwise Strategy toward Tetracyclic Fused Heterocycles
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Palladium-catalyzed intramolecular tandem cyclization reactions were conducted for the synthesis of densely cis/cis-fused aza-tetracyclic structures. The process involved a palladium(II)-catalyzed aerobic aza-Wacker reaction, followed by a palladium(0)-catalyzed Heck reaction. The effects of the solvent and benzene substitution pattern on the one-pot, two-step cascade reaction were studied systematically, and a probable mechanism was proposed. Strained pentahydrobenzo[f]cyclopenta[hi]indolizin-6-one and racemic γ-lycorane can also be synthesized rapidly using this palladium-catalyzed aza-Wacker-Heck cyclization reaction.
- Chen, Li-Yuan,Chuang, Ta-Hsien,Lai, Chin-Hung,Tang, Rong-Shiow
-
supporting information
p. 9337 - 9341
(2020/12/21)
-
- Utilization of BozPhos as an Effective Ligand in Enantioselective C-H Functionalization of Cyclopropanes: Synthesis of Dihydroisoquinolones and Dihydroquinolones
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The bisphosphine monoxide (R,R)-BozPhos enables enantioselective C-H functionalization of cyclopropanes in a palladium-catalyzed cyclization. The synthesis of a broad spectrum of dihydroisoquinolones and dihydroquinolones in good yields and high enantiomeric excess was achieved through the use of this hemilabile ligand. Furthermore, the isolation of an intermediary palladium(II)-BozPhos complex after oxidative addition was successful and a second complex provided further insight into bond length and angles through a crystal structure.
- Mayer, Camilla,Ladd, Carolyn L.,Charette, André B.
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supporting information
p. 2639 - 2644
(2019/04/17)
-
- Method for synthesizing chlorantraniliprole derivative intermediate
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The invention provides a method for synthesizing a chlorantraniliprole derivative intermediate, belonging to the field of agricultural pesticides. The method comprises the following steps: subjectingthe intermediate 3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylic acid to chlorination so as to prepare 3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-formyl chloride; subjecting the raw material 2-bromobenzoic acid to acylating chlorination and ammoniation so as to prepare substituted 2-bromo-benzamide; and subjecting 3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-formyl chloride and substituted 2-bromo-benzamide to cyclization so as to obtain the chlorantraniliprole derivative intermediate. The method of the invention is simple and common; reagents used in the process of synthesis are low in toxicity, used solvents are recyclable, and few by-products are produced, so the method has little corrosion to equipment and low pollution to environment; since raw materials are cheap, production cost is reduced and good economical efficiency is obtained; therefore, the method has good application prospects.
- -
-
Paragraph 0024; 0025
(2018/04/02)
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- C-H to C-N Cross-Coupling of Sulfonamides with Olefins
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Cross-coupling of nitrogen with hydrocarbons under fragment coupling conditions stands to significantly impact chemical synthesis. Herein, we disclose a C(sp3)-N fragment coupling reaction between terminal olefins and N-triflyl protected aliphatic and aromatic amines via Pd(II)/SOX (sulfoxide-oxazoline) catalyzed intermolecular allylic C-H amination. A range of (56) allylic amines are furnished in good yields (avg. 75%) and excellent regio- and stereoselectivity (avg. >20:1 linear:branched, >20:1 E:Z). Mechanistic studies reveal that the SOX ligand framework is effective at promoting functionalization by supporting cationic π-allyl Pd.
- Ma, Rulin,Christina White
-
supporting information
p. 3202 - 3205
(2018/03/13)
-
- Scope and mechanism of a true organocatalytic beckmann rearrangement with a boronic acid/perfluoropinacol system under ambient conditions
-
Catalytic activation of hydroxyl functionalities is of great interest for the production of pharmaceuticals and commodity chemicals. Here, 2-alkoxycarbonyl- and 2-phenoxycarbonyl-phenylboronic acid were identified as efficient catalysts for the direct and chemoselective activation of oxime N-OH bonds in the Beckmann rearrangement. This classical organic reaction provides a unique approach to prepare functionalized amide products that may be difficult to access using traditional amide coupling between carboxylic acids and amines. Using only 5 mol % of boronic acid catalyst and perfluoropinacol as an additive in a polar solvent mixture, the operationally simple protocol features mild conditions, a broad substrate scope, and a high functional group tolerance. A wide variety of diaryl, aryl-alkyl, heteroaryl-alkyl, and dialkyl oximes react under ambient conditions to afford high yields of amide products. Free alcohols, amides, carboxyesters, and many other functionalities are compatible with the reaction conditions. Investigations of the catalytic cycle revealed a novel boron-induced oxime transesterification providing an acyl oxime intermediate involved in a fully catalytic nonself-propagating Beckmann rearrangement mechanism. The acyl oxime intermediate was prepared independently and was subjected to the reaction conditions. It was found to be self-sufficient; it reacts rapidly, unimolecularly without the need for free oxime. A series of control experiments and 18O labeling studies support a true catalytic pathway involving an ionic transition structure with an active and essential role for the boronyl moiety in both steps of transesterification and rearrangement. According to 11B NMR spectroscopic studies, the additive perfluoropinacol provides a transient, electrophilic boronic ester that is thought to serve as an internal Lewis acid to activate the ortho-carboxyester and accelerate the initial, rate-limiting step of transesterification between the precatalyst and the oxime substrate.
- Mo, Xiaobin,Morgan, Timothy D. R.,Ang, Hwee Ting,Hall, Dennis G.
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supporting information
p. 5264 - 5271
(2018/04/24)
-
- Copper-Catalyzed Cascade Synthesis of [1,2,4]-Triazoloquinazolinones
-
An efficient and practical method for the synthesis of 1,2,4-triazolo[5,1- b ]quinazolin-9(3 H)-ones has been developed via the copper-catalyzed domino reactions of readily available substituted N ′-acetyl-2-bromobenzohydrazides with cyanamide. The protocol uses inexpensive CuI as the catalyst, and no other ligand or additive was required. The target products were prepared in good to excellent yields with tolerance of various functional groups.
- Lou, Zhenbang,Man, Ningning,Yang, Haijun,Zhu, Changjin,Fu, Hua
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supporting information
p. 1395 - 1399
(2018/05/03)
-
- Palladium-Catalyzed Enantioselective Intramolecular Dearomative Heck Reaction
-
Enantioselective intramolecular dearomative Heck reactions have been developed by Pd-catalyzed cross-coupling of aryl halides or aryl triflates with the internal C=C bond of indoles, benzofurans, pyrroles, and furans. A variety of structurally unique spir
- Li, Xiang,Zhou, Bo,Yang, Run-Ze,Yang, Fu-Ming,Liang, Ren-Xiao,Liu, Ren-Rong,Jia, Yi-Xia
-
supporting information
p. 13945 - 13951
(2018/10/20)
-
- Mechanism of Acylative Oxidation-Reduction-Condensation Reactions Using Benzoisothiazolones as Oxidant and Triethylphosphite as Stoichiometric Reductant
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We previously described a new organocatalytic oxidation-reduction-condensation for amide/peptide construction. The reaction system relies on triethylphosphite as the stoichiometric reductant and organocatalytic benzoisothiazolone/O2 in air as the oxidant. The reaction was assumed to generate catalytic quantities of S-acylthiosalicylamides as electrophiles, which are rapidly intercepted by amine reactants to generate amides/peptides and o-mercaptobenzamides. The latter are then gently reoxidized to the benzoisothiazolones under Cu-catalyzed aerobic conditions to complete the catalytic cycle. To gain a mechanistic understanding, we describe herein our studies of the stoichiometric generation of S-acylthiosalicylamides under oxidation-reduction-condensation conditions from a variety of benzoisothiazolones and carboxylic acids using triethylphosphite as the terminal reductant. These studies have revealed the presence of more than one reaction pathway when benzoisothiazolones react with triethylphosphite (including a rapid, direct deoxygenation of certain classes of benzoisothiazolones by triethylphosphite) and allow the identification of optimal reaction characteristics (benzoisothiazolone structure and solvent) for the generation of thioesters. These explorations will inform our efforts to develop highly effective and robust organocatalytic oxidation-reduction-condensation reactions that are based on the benzoisothiazolone and related motifs.
- Gangireddy, Pavankumar,Patro, Vidyavathi,Lam, Leighann,Morimoto, Mariko,Liebeskind, Lanny S.
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p. 3513 - 3529
(2017/04/11)
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- Anthraquinone compound and its preparation method and medical use (by machine translation)
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The invention relates to a anthraquinone compound and its preparation method and medical use, cheap and easy to get to the isophthalic acid as the starting material, through the bromo, hydrolysis, esterification of the obtained intermediate with 2 - bromo - 5 - methoxy acyl chloride condensation, condensation product after hydrolysis, loop, debromination reduction to obtain the target product 1, 5 - dihydroxy - 3 - carboxyl - 9, 10 - anthraquinone. The reaction of the invention cheap, low cost, simple operation, high yield. Anti-tumor activity study results display, artificial synthesis of 1, 5 - dihydroxy - 3 - carboxyl - 9, 10 - anthraquinone has better anti-tumor activity. (by machine translation)
- -
-
Paragraph 0006; 0012
(2017/08/30)
-
- Synthesis and neuroprotective activity of dictyoquinazol A and analogues
-
A flexible and efficient synthesis of the neuroprotective alkaloid, dictyoquinazol A, is reported. Several structural analogues of the target molecule were produced, and the neuroprotective activity of this series of compounds was investigated using three
- Lizarme, Yuvixza,Wangsahardja, Jonatan,Marcolin, Gabriella M.,Morris, Jonathan C.,Jones, Nicole M.,Hunter, Luke
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p. 1480 - 1487
(2016/03/16)
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- Microwave assisted synthesis of phenanthridinones and dihydrophenanthridines by vasicine/KO: T Bu promoted intramolecular C-H arylation
-
A simple, efficient, rapid and transition metal-free methodology has been developed by utilizing vasicine (a natural product), as a catalyst for the synthesis of phenanthridinones and dihydrophenanthridines. The reaction proceeds through intramolecular C-H arylation with aryl halides in the presence of KOtBu as a base under microwave irradiation in sulfolane as a solvent. The reaction proceeds well with various aryl iodides, bromides and more remarkably with less reactive aryl chlorides for 15 minutes, providing the corresponding products in 45-90% yields.
- Sharma, Sushila,Kumar, Manoranjan,Sharma, Shruti,Nayal, Onkar S.,Kumar, Neeraj,Singh, Bikram,Sharma, Upendra
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p. 8536 - 8544
(2016/09/28)
-
- FUSED AZOLE DERIVATIVE
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The present invention provides agents for treating or preventing diseases such as mood disorder, anxiety disorder, schizophrenia, Alzheimer's disease, Parkinson's disease, Huntington's chorea, eating disorder, hypertension, gastrointestinal disease, drug addiction, epilepsy, cerebral infarction, cerebral ischemia, cerebral edema, head injury, inflammation, immune-related disease, alopecia. Specifically, the invention provides fused azole derivatives represented by general formula (I) or pharmaceutically acceptable salts thereof that have an antagonistic action against the arginine-vasopressin 1b receptor:
- -
-
Paragraph 0474-0476
(2015/02/25)
-
- Facile synthesis of 1-naphthols through a copper-catalyzed arylation of methyl ketones with o-bromoacetophenones
-
The coupling reactions of simple methyl ketones with o-bromoacetophenones and subsquential cyclization reactions were realized to produce a range of 1-naphthols. These cascade reactions were initiated by a rare Cu-catalyzed arylation reaction of methyl ketones with aromatic bromides.
- Lou, Zhen-Bang,Pang, Xin-Long,Chen, Chao,Wen, Li-Rong,Li, Ming
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supporting information
p. 1231 - 1235
(2015/12/30)
-
- Synthesis of novel 1,4-disubstituted 1,2,3-triazolo-bosentan derivatives - evaluation of antimicrobial and anticancer activities and molecular docking
-
Novel 1,4-disubstituted 1,2,3-triazolo bosentan derivatives 1a-n from bosentan 2 were synthesized in good yields by sequential chlorination, azidation followed by Cu(i) catalyzed 1,3-dipolar cycloaddition. All obtained compounds 1a-n were evaluated for their antimicrobial and in vitro anticancer activities and by in silico docking studies. Among all tested compounds 1e,f and 1h-j show better antimicrobial activities against the tested bacteria and fungi. When subjected to anticancer testing, compounds 1g-j and 1n show significant activities against both A549 and SKOV-3 cell lines with IC50 values at 7.81 μg mL-1 and among them compound 1i exhibited very potent activity. In addition, no toxicity was calculated up to 2 mg mL-1 in Vero cells. In silico studies were conducted to investigate the possible bonding modes of 1a-n with target receptors namely DNA topoisomerase IV (4 EMV) and anaplastic lymphoma kinase (2XP2). Among them, compounds 1e and 1h show maximum binding energies with 4EMV and 2XP2 receptors, respectively which also exhibited good antimicrobial and potent anticancer activities.
- Easwaramoorthi,Rajendran, A. Jeya,Rao, K. Chennakesava,Arun,Balachandran,Perumal,Emi, Nobuhiko,Mahalingam,Duraipandiyan,Al-Dhabi
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p. 105266 - 105278
(2015/12/30)
-
- 2,5-Bis(2-(diphenylphosphino)phenyl)-1,3,4-oxadiazole ligands and their Cu(I) complexes for Sonogashira coupling reaction
-
Two diphosphane ligands - 2,5-bis(2-(diphenylphosphino)-5-R)phenyl)-1,3,4- oxadiazole (L1, R = H, L2, R = OMe) and their binuclear complexes, L1Cu and L2Cu, were prepared and characterized. The molecular structures of L1Cu and L2Cu, as perchlorate salts,
- Lin, Cai-Xia,Zhu, Jia-Fang,Li, Qing-Shan,Ao, Li-Hua,Jin, Yan-Juan,Xu, Feng-Bo,Hu, Fang-Zhong,Yuan, Yao-Feng
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p. 298 - 303
(2014/04/03)
-
- Synthesis of 5-methyl phenanthridium derivatives: A new class of human DOPA decarboxylase inhibitors
-
DOPA decarboxylase (DDC) is responsible for the decarboxylation of l-DOPA and related aromatic amino acids and correlates closely with a number of clinical disorders. Sanguinarine, a natural quaternary benzophenanthridine alkaloid (QBA), was reported to b
- Cheng, Pi,Zhou, Jie,Qing, Zhixing,Kang, Weisong,Liu, Sheng,Liu, Wei,Xie, Hongqi,Zeng, Jianguo
-
supporting information
p. 2712 - 2716
(2014/06/09)
-
- Enantioselective synthesis of planar chiral ferrocenes via Pd(0)-catalyzed intramolecular direct C-H bond arylation
-
A highly efficient synthesis of planar chiral ferrocenes by enantioselective Pd(0)-catalyzed direct C-H arylation from readily available starting materials under mild reaction conditions was developed (up to 99% yield, 99% ee). The products can be easily transformed to the highly efficient planar ferrocene ligands, which have demonstrated high efficiency in Pd-catalyzed asymmetric allylic alkylation and amination reactions.
- Gao, De-Wei,Yin, Qin,Gu, Qing,You, Shu-Li
-
supporting information
p. 4841 - 4844
(2014/04/17)
-
- Synthesis of 1-indanols and 1-indanamines by intramolecular palladium(0)-catalyzed C(sp3)-H arylation: Impact of conformational effects
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A range of valuable 1-indanols and 1-indanamines containing a tertiary C1 atom were synthesized by intramolecular palladium(0)-catalyzed C(sp 3)-H arylation, despite unfavorable steric interactions. The efficiency of the reaction was found to correlate with the degree of substitution at C2, as expected from the Thorpe-Ingold effect. Additionally, the nature of the heteroatomic substituent at C1 had a marked influence on the diastereoselectivity at C1 and C2; indeed, 1-indanols and 1-indanamines were obtained with the opposite relative configuration. Analysis of the X-ray and DFT-optimized structures of the corresponding reactive intermediates provided useful insights into the subtle conformational effects induced by these substituents.
- Janody, Simon,Jazzar, Rodolphe,Comte, Arnaud,Holstein, Philipp M.,Baudoin, Olivier,Vors, Jean-Pierre,Ford, Mark J.
-
supporting information
p. 11084 - 11090,7
(2014/10/15)
-
- Synthesis of 5-methyl phenanthridium derivatives: A new class of human DOPA decarboxylase inhibitors
-
DOPA decarboxylase (DDC) is responsible for the decarboxylation of l-DOPA and related aromatic amino acids and correlates closely with a number of clinical disorders. Sanguinarine, a natural quaternary benzophenanthridine alkaloid (QBA), was reported to b
- Cheng, Pi,Zhou, Jie,Qing, Zhixing,Kang, Weisong,Liu, Sheng,Liu, Wei,Xie, Hongqi,Zeng, Jianguo
-
supporting information
p. 2712 - 2716
(2015/02/19)
-
- Nickel or phenanthroline mediated intramolecular arylation of sp 3 C-H bonds using aryl halides
-
The development of the intramolecular arylation of sp3 C-H bonds adjacent to nitrogen using aryl halides is described. Arylation was accomplished using either Ni(COD)2 or 1,10-phenanthroline in substoichiometric amounts, and the reaction conditions were applied to a variety of electronically differentiated benzamide substrates. Preliminary studies suggest a mechanism involving aryl and alkyl radical intermediates.
- Wertjes, William C.,Wolfe, Lydia C.,Waller, Peter J.,Kalyani, Dipannita
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supporting information
p. 5986 - 5989
(2014/01/06)
-
- Design, synthesis, and applications of potential substitutes of t-Bu-phosphinooxazoline in Pd-catalyzed asymmetric transformations and their use for the improvement of the enantioselectivity in the Pd-catalyzed allylation reaction of fluorinated allyl enol carbonates
-
The design, synthesis, and applications of potential substitutes of t-Bu-PHOX in asymmetric catalysis is reported. The design relies on the incorporation of geminal substituents at C5 in combination with a substituent at C4 other than t-butyl (i-Pr, i-Bu, or s-Bu). Most of these new members of the PHOX ligand family behave similarly in terms of stereoinduction to t-Bu-PHOX in three palladium-catalyzed asymmetric transformations. Electronically modified ligands were also prepared and used to improve the enantioselectivity in the Pd-catalyzed allylation reaction of fluorinated allyl enol carbonates.
- Belanger, Etienne,Pouliot, Marie-France,Courtemanche, Marc-Andre,Paquin, Jean-Francois
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experimental part
p. 317 - 331
(2012/02/15)
-
- An efficient copper mediated synthetic methodology for benzo[d]isothiazol- 3(2H)-ones and related sulfur-nitrogen heterocycles
-
A copper mediated sulfur-nitrogen coupling reaction for the synthesis of benzo[d]isothiazol-3(2H)-ones and related sulfur-nitrogen heterocycles has been presented, which requires 2-halo-arylamides, sulfur powder, 25-50 mol % of copper iodide/1,10-phenanthroline, and potassium carbonate as base.
- Bhakuni, Bhagat Singh,Balkrishna, Shah Jaimin,Kumar, Amit,Kumar, Sangit
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supporting information; body text
p. 1354 - 1357
(2012/04/10)
-
- Intramolecular direct dehydrohalide coupling promoted by KOtBu: Total synthesis of amaryllidaceae alkaloids anhydrolycorinone and oxoassoanine
-
A transition-metal-free intramolecular dehydrohalide coupling via intramolecular homolytic aromatic substitution (HAS) with aryl radicals has been developed in the presence of potassium tert-butoxide and an organic molecule as the catalyst. The methodology has been applied to a concise synthesis of Amaryllidaceae alkaloids viz. oxoassoanine (1b), anhydrolycorinone (1d), and other related structures. Interestingly, the method also works only in the presence of potassium tert-butoxide.
- De, Subhadip,Ghosh, Santanu,Bhunia, Subhajit,Sheikh, Javeed Ahmad,Bisai, Alakesh
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supporting information
p. 4466 - 4469
(2012/10/29)
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- FATTY ACID AMIDE HYDROLASE INHIHIBITORS FOR TREATING PAIN
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Compounds of Formula 1 are described herein. These compounds may be administered to a patient for treatment of suffering from pain or other FAAH mediated conditions.
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Page/Page column 20
(2012/11/07)
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- Microwave assisted copper-free Sonogashira coupling/5-exo-dig cycloisomerization domino reaction: Access to 3-(phenylmethylene)isoindolin-1- ones and related heterocycles
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An efficient microwave assisted one-pot synthesis of substituted 3-(phenylmethylene)isoindolin-1-ones is reported via a copper-free Sonogashira coupling and a regioselective 5-exo-dig cycloisomerization. This domino reaction was also extended to other related heterocycles.
- Hellal, Malik,Cuny, Gregory D.
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supporting information; experimental part
p. 5508 - 5511
(2011/10/31)
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- Enantioselective synthesis of axially chiral biaryls by the pd-catalyzed suzuki-miyaura reaction: Substrate scope and quantum mechanical investigations
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We report efficient syntheses of axially chiral biaryl amides in yields ranging from 80-92%, and with enantioselectivity in the range 88-94% ee employing an asymmetric Suzuki-Miyaura process with Pd(OAc)2 and KenPhos as ligand. These studies demonstrate that electron-rich and electron-deficient o-halobenzamides can be efficiently coupled with 2-methyl-1-naphthylboronic acid and 2-ethoxy-1-naphthylboronic acid. The yields and selectivities of the reactions are independent of the nature of halogen substituent on the benzamide coupling partner. Our investigations demonstrate that axially chiral heterocyclic and biphenyl compounds can also be synthesized with this methodology. We also report computational studies used to determine the origin of stereoselectivity during the selectivity-determining reductive elimination step of the related coupling of tolyl boronic acid with naphthylphosphonate bromide that was reported in a previous publication (J. Am. Chem. Soc. 2000, 122, 12051-12052). These studies indicate that the stereoselectivity arises from a combination of weak -(C)H??O interactions as well as steric interactions between the tolyl and naphthylphosphonate addends in the transition state for C-C coupling.
- Shen, Xiaoqiang,Jones, Gavin O.,Watson, Donald A.,Bhayana, Brijesh,Buchwald, Stephen L.
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supporting information; experimental part
p. 11278 - 11287
(2010/10/04)
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- Investigation of the mechanism of C(sp3)-H bond cleavage in Pd(0)-catalyzed intramolecular alkane arylation adjacent to amides and sulfonamides
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The reactivity of C(sp3)-H bonds adjacent to a nitrogen atom can be tuned to allow intramolecular alkane arylation under Pd(0) catalysis. Diminishing the Lewis basicity of the nitrogen lone pair is crucial for this catalytic activity. A range of N-methylamides and sulfonamides react exclusively at primary C(sp3)-H bonds to afford the products of alkane arylation in good yields. The isolation of a Pd(II) reaction intermediate has enabled an evaluation of the reaction mechanism with a focus on the role of the bases in the C(sp3)-H bond cleaving step. The results of these stoichiometric studies, together with kinetic isotope effect experiments, provide rare experimental support for a concerted metalation-deprotonation (CMD) transition state, which has previously been proposed in alkane C(sp3)-H arylation. Moreover, DFT calculations have uncovered the additional role of the pivalate additive as a promoter of phosphine dissociation from the Pd(II) intermediate, enabling the CMD transition state. Finally, kinetic studies were performed, revealing the reaction rate expression and its relationship with the concentration of pivalate.
- Rousseaux, Sophie,Gorelsky, Serge I.,Chung, Benjamin K. W.,Fagnou, Keith
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supporting information; experimental part
p. 10692 - 10705
(2010/11/05)
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- Radical-initiated cyclization as a key step for the synthesis of oxoprotoberberine alkaloids
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The oxoprotoberberine alkaloids 1a-d have been synthesized efficiently from the enamide derivatives 2a-d by a radical-initiated cyclization reaction utilizing n-Bu3SnH/AIBN and CuCl. The enamide derivatives 2a-d were prepared from phenylethylam
- Lee, Chih-Shone,Yu, Tsung-Ching,Luo, Jian-Wen,Cheng, Yen-Yao,Chuang, Che-Ping
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scheme or table
p. 4558 - 4562
(2009/12/03)
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- Efficient synthesis of phenanthridinone derivatives via a palladium-catalyzed coupling process
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(Chemical Equation Presented) A palladium-mediated domino reaction was developed to conveniently synthesize phenanthridinone derivatives. Phosphine ligand 1 strongly promotes the domino process, which includes aryl-aryl coupling and C-N bond formations concomitant with a deamidation reaction. The versatility and applicability to a broad range of substrates make this reaction useful for the development of bioactive derivatives.
- Furuta, Takumi,Kitamura, Yuki,Hashimoto, Ayano,Fujii, Satoshi,Tanaka, Kiyoshi,Kan, Toshiyuki
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p. 183 - 186
(2007/10/03)
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- Synthesis of 3-substituted indazoles and benzoisoxazoles via Pd-catalyzed cyclization reactions: application to the synthesis of nigellicine
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Syntheses of 3-substituted indazoles and benzoisoxazoles were efficiently accomplished with the aid of Pd-catalyzed intramolecular carbon-nitrogen and carbon-oxygen bond formations. The catalyst system described herein allows the cyclization to proceed under very mild conditions and thus could be applied to a wide range of substrates with acid- or base-sensitive functional groups. A total synthesis for the indazole ring-containing natural product nigellicine is also described.
- Inamoto, Kiyofumi,Katsuno, Mika,Yoshino, Takashi,Arai, Yukari,Hiroya, Kou,Sakamoto, Takao
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p. 2695 - 2711
(2007/10/03)
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- Cationic chalcone antibiotics. Design, synthesis, and mechanism of action
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This paper describes how the introduction of "cationic" aliphatic amino groups in the chalcone scaffold results in potent antibacterial compounds. It is shown that the most favorable position for the aliphatic amino group is the 2-position of the B-ring, in particular in combination with a lipophilic substituent in the 5-position of the B-ring. We demonstrate that the compounds act by unselective disruption of cell membranes. Introduction of an additional aliphatic amino group in the á-ring results in compounds that are selective for bacterial membranes combined with a high antibacterial activity against both Gram-positive and -negative pathogens. The most potent compound in this study (78) has an MIC value of 2 μM against methicillin resistant Staphylococus aureus.
- Nielsen, Simon F.,Larsen, Mogens,Boesen, Thomas,Sch?nning, Kristian,Kromann, Hasse
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p. 2667 - 2677
(2007/10/03)
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- Nickel(II) complexes bearing phosphinooxazoline ligands: Synthesis, structures and their ethylene oligomerization behaviors
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A series of Ni(II) complexes 4a-f ligated by the unsymmetrical phosphino-oxazolines (PHOX) were synthesized and characterized by elemental analysis and IR spectroscopy, and the structures of complexes 4c-4e were confirmed by the X-ray crystallographic analysis. All derivatives showed distorted tetrahedron geometry by the nickel center and coordinative atoms. Upon activation with methylaluminoxane (MAO) or Et2AlCl, these complexes exhibited considerable to high activity of ethylene oligomerization. The ligands environments and reaction conditions significantly affect their catalytic activities, while the highest oligomerization activity (up to 1.18 × 106 g ? mol-1(Ni) ? h-1) was observed for 4d at 20 atm of ethylene. Incorporation of 2-4 equivalents of PPh 3 as auxiliary ligands in the 4a-f/MAO catalytic systems led to higher activity and longer catalytic lifetime.
- Tang, Xiubo,Zhang, Dongheng,Jie, Suyun,Sun, Wen-Hua,Chen, Jiutong
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p. 3918 - 3928
(2007/10/03)
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- BICYCLIC IMIDAZOL DERIVATIVES AGAINST FLAVIVIRIDAE
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Disclosed are compounds, compositions and methods for treatingFlaviviridae family virus infections.
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Page/Page column 211-212
(2008/06/13)
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- SELECTIVE ESTROGEN RECEPTOR MODULATORS
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The present invention provides a compound represented by the following formula (I); [wherein T represents a single bond, a C1-C4 alkylene group which may have a substituent and the like; formula (I-1) represents a single bond or a double bond; A represents a single bond, a bivalent 5- to 14-membered heterocyclic group which may have a substituent and the like; Y represents a single bond and the like; Z represents a methylene group and the like; ring G represents a phenylene group and the like which may condense with a 5- to 6-membered ring and may have a heteroatom; Ra and Rb are the same as or different from each other and represent a hydrogen atom and the like; W represents a single bond and the like; R' represents 1 to 4 independent hydrogen atoms and the like; and R" represents 1 to 4 independent hydrogen atoms and the like] or a salt thereof, or a hydrate thereof.
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Page/Page column 114
(2008/06/13)
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- Heteropolycyclic compounds and their use as metabotropic glutamate receptor antagonists
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The present invention provides compounds and pharmaceutical compositions that act as antagonists at metabotropic glutamate receptors, and that are useful for treating neurological diseases and disorders. Methods of preparing the compounds also are disclosed.
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- A versatile synthesis of poly- and diversely substituted isoindolin-1- ones
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A variety of diversely substituted isoindolin-1-ones have been prepared by alkaline cleavage of the C-P bond in the corresponding phosphorylated lactams obtained by base-induced aryne-mediated cyclization of o-halogeno-N- (phosphinylmethyl)benzamide derivatives.
- Hoarau, Christophe,Couture, Axel,Deniau, Eric,Grandclaudon, Pierre
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p. 655 - 660
(2007/10/03)
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- Synthesis of an (Imidazopyrimidin-2-yl) Phenylethanol Derivative as a Sulmazole-Pronethalol Hybrid Model
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A potentially versalite route to the racemic title compound (3) utylising an ortho-acetyl(bromoacetyl)benzene monoketal intermediate (26) is described.This methodology avoids problems associated with the tautomerism of ortho-acetylbenzoic acid derivatives
- Barraclough, Paul,Smith, Steven
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p. 526 - 541
(2007/10/02)
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- Dibenzocyclooctene-, Dibenzochalcocine-, and Diarenochalconinediones
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2,2'-Oxybis-, -thiobis-, and -methylenebisbenzoic esters 2a-c react with methyllithium in ether to give low yields of 5H-dibenzochalcocine-5,7(6H)-diones 6a, 7a, and dibenzocyclooctene-5,7(6H,12H)-dione (8), respectively.Very good yields of such heterocycles with oxygen (6a-h, 37), sulfur (7a-h, 38) and selenium (36) as key atom are obtained when diaryl ethers (21, 22, 25), -sulfides (27, 29, 30), and -selenides (33) that contain 2'-acetyl- (or -propionyl-) and 2-methoxycarbonyl groups are treated with sodium hydride in boiling toluene.Analogously are prepared the dibenzoxonine-11,13(6H,12H)diones 62a-c and 7H-benzonaphthothionine-7,9-(8H)-dione (65) which are expanded by one ring member.In the analogous reaction of a corresponding benzophenone derivative 35, spiro-3(2H),3'-dione (41) is formed in a tandem reaction. - Under phase transfer conditions the dibenzochalcocinediones 6, 7, 36 and also the corresponding nitrogen cycles 5 react to give mixtures of C- (42-45) and O-alkyl derivatives (46-49).Methyllithium and diisobutylaluminium hydride provide the carbinols 50-54.With bromine and SO2Cl2, respectively, the methylene group is mono- or dihalogenated to the products 56, 57; defined nitration was only possible for the oxacycle 6a.
- Hellwinkel, Dieter,Bohnet, Siegbert
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p. 1151 - 1174
(2007/10/02)
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