- A facile and versatile electro-reductive system for hydrodefunctionalization under ambient conditions
-
A general electrochemical system for reductive hydrodefunctionalization is described, employing the inexpensive and easily available triethylamine (Et3N) as a sacrificial reductant. This protocol is characterized by facile operation, sustainable conditions, and exceptionally wide substrate scope covering the cleavage of C-halogen, N-S, N-C, O-S, O-C, C-C and C-N bonds. Notably, the selectivity and capability of reduction can be conveniently switched by simple incorporation or removal of an alcohol as a co-solvent.
- Huang, Binbin,Guo, Lin,Xia, Wujiong
-
supporting information
p. 2095 - 2103
(2021/03/26)
-
- Method for synthesizing aryl benzyl ether compound
-
The invention discloses a method for synthesizing aryl benzyl ether compounds, which comprises the following steps: by using an iron (III) complex containing 1, 3-di-tert-butyl imidazole cations and having a molecular formula of [(tBuNCH = CHNtBu) CH] [FeBr4] as a catalyst and di-tert-butyl peroxide as an oxidant, carrying out oxidative coupling reaction on phenolic compounds and toluene compounds to synthesize the corresponding aryl benzyl ether compounds. The method is the first example for preparing the aryl benzyl ether compound through the oxidative coupling reaction of the phenolic compound and the toluene compound, which is realized by an iron-based catalyst, and has the advantages of atom economy, environmental friendliness and good substrate applicability.
- -
-
Paragraph 0033; 0041
(2021/04/14)
-
- Application of iron (III) complex containing 1,3-di-tert-butyl imidazole cations in synthesis of aryl benzyl ether compounds
-
The invention discloses an application of an iron (III) complex containing 1,3-di-tert-butyl imidazole cations in synthesis of aryl benzyl ether compounds, and particularly relates to a method for synthesizing corresponding aryl benzyl ether compounds by taking di-tert-butyl peroxide as an oxidizing agent and carrying out oxidative coupling reaction on phenolic compounds and toluene compounds. According to the method, the iron (III) complex is used as the catalyst for the first time, and oxidative coupling of the phenolic compound and the toluene compound is realized. The method is the first oxidative coupling reaction of phenolic compounds and benzyl C(sp3)-H bonds, and a new method is provided for synthesizing aryl benzyl ether compounds. Compared with an existing synthesis method, the method provided by the invention avoids using toxic and polluting halogenated hydrocarbon and strong base, has better atom economy, and conforms to the development concept of green synthetic chemistry.
- -
-
Paragraph 0032-0033
(2021/04/26)
-
- 3BéTA-(BENZYLOXY)-17ALPHA-METHYL-PREGN-5-EN-20-ONE FOR USE IN THE TREATMENT OF COGNITIVE DISORDERS
-
The present invention generally relates to a specific pregnenolone derivative for its use for the treatment of a cognitive disorders. More particularly, the invention relates to a compound of Formula (I) for its use in the treatment of cognitive disorders. Indeed, the compound of the invention is in vivo very potent in correcting the cognitive impairments observed in cognitive disorders.
- -
-
Paragraph 0021
(2020/07/07)
-
- Decyanative Cross-Coupling of Cyanopyrimidines with O-, S-, and N-Nucleophiles: A Route to Alkoxylpyrimidines, Aminopyrimidines and Alkylthiopyrimidines
-
The transition metal-free cross-coupling reactions of cyanopyrimidines with aliphatic alcohols, thiols (or S-alkylisothiourea salts) and amines, giving the corresponding alkoxylpyrimidines, aminopyrimidines, and alkylthiopyrimidines, are reported. Prelimi
- Wei, Xiangyang,Zhang, Caiyang,Wang, Yifei,Zhan, Qi,Qiu, Guiying,Fan, Ling,Yin, Guodong
-
p. 7142 - 7150
(2019/11/14)
-
- Environmentally benign nucleophilic substitution reaction of arylalkyl halides in water using CTAB as the inverse phase transfer catalyst
-
An environmentally benign, practically scalable and highly selective C-arylalkylation of active methylene compounds is developed using CTAB as the inverse phase transfer catalyst in water. The methodology developed is elaborated into the one-pot synthesis of quinoline derivatives and also applicable to the regioselective N-aralkyl of 2-pyridones.
- Godha, Atul K.,Thiruvengadam, Jayaraman,Abhilash, Viswanadhan,Balgi, Prajwal,Narayanareddy,Vignesh, Kumaresan,Gadakh, Amol V.,Sathiyanarayanan,Ganesh, Sambasivam
-
p. 16041 - 16045
(2019/10/28)
-
- Zinc (II)-mediated selective O-benzylation of 2-Oxo-1,2-dihydropyridines systems
-
The selective O-benzylation of 2-oxo-1,2-dihydropyridines plays a critical role in organic synthesis of natural products and biological active molecules. Herein we report a novel ternary system of ZnO, ZnCl2 and N,N-diisopropylethylamine (DIEA), that is highly effective for selective O-benzylation of 2-oxo-1,2-dihydropyridines using abundant substituted benzyl halides and related substituted 2-oxo-1,2-dihydropyridines compounds. This process allows access to a variety of O-benzyl products under mild reaction conditions, which are important synthetic intermediates in the protection of functional groups, and represents a new method toward the development for the O-benzylation of 2-oxo-1,2-dihydropyridines.
- Zhou, Qifan,Du, Fangyu,Liang, Xinjie,Liu, Wenqiang,Fang, Ting,Chen, Guoliang
-
-
- Carbon–Fluorine Reductive Elimination from Nickel(III) Complexes
-
We report a C?F reductive elimination from a characterized first-row aryl metal fluoride complex. Reductive elimination from the presented nickel(III) complexes is faster than C?F bond formation from any other characterized aryl metal fluoride complex.
- Lee, Heejun,B?rgel, Jonas,Ritter, Tobias
-
supporting information
p. 6966 - 6969
(2017/06/06)
-
- Photoreductive Removal of O-Benzyl Groups from Oxyarene N-Heterocycles Assisted by O-Pyridine-pyridone Tautomerism
-
Facile photoreductive protocols have been developed to remove benzyl O-protective groups from oxyarene N-heterocycles at positions capable for 2-/4-O-pyridine-2-/4-pyridone tautomerism. Blue light irradiation, a [Ru] or [Ir] photocatalyst, and ascorbic acid in a water-acetonitrile solution debenzylates a variety of aryl N-heterocycles cleanly and selectively. Ascorbic acid has two functions in the reaction. On the one hand, it protonates the N-heterocycles that reduces their reduction potentials notably and on the other hand it acts as a sacrificial reductant. Reduction potentials and free energy barriers calculated at the CPCM-B3LYP/6-31+G? level can predict the reactivities of the studied substrates.
- Todorov, Aleksandar R.,Wirtanen, Tom,Helaja, Juho
-
p. 13756 - 13767
(2017/12/26)
-
- Mild and Regioselective N-Alkylation of 2-Pyridones in Water
-
A mild and regioselective N-alkylation reaction of 2-pyridones in water has been developed. Tween 20 (2% w/w) was added to create a micellar system for improved solubility of starting materials, which leads to enhanced reaction rates. The protocol demonstrated a wide substrate scope with good isolated yields (40-94%) for all of the 24 examples evaluated. High regioselectivity favoring N-alkylation over O-alkylation was observed for benzyl halides (>5:1), primary alkyl halides (>6:1), and bulky and less reactive secondary alkyl halides (>2.4:1).
- Hao, Xin,Xu, Zhongmiao,Lu, Hongfu,Dai, Xuedong,Yang, Ting,Lin, Xichen,Ren, Feng
-
supporting information
p. 3382 - 3385
(2015/07/28)
-
- Development of novel selective peptidomimetics containing a boronic acid moiety, targeting the 20s proteasome as anticancer agents
-
This paper describes the design, synthesis, and biological evaluation of peptidomimetic boronates as inhibitors of the 20S proteasome, a validated target in the treatment of multiple myeloma. The synthesized compounds showed a good inhibitory profile against the ChT-L activity of 20S proteasome. Compounds bearing a β-alanine residue at the P2 position were the most active, that is, 3-ethylphenylamino and 4-methoxyphenylamino (R)-1-{3-[4-(substituted)-2- oxopyridin-1(2H)-yl]propanamido}-3-methylbutylboronic acids (3 c and 3 d, respectively), and these derivatives showed inhibition constants (Ki) of 17 and 20 nM, respectively. In addition, they co-inhibited post glutamyl peptide hydrolase activity (3 c, Ki=2.57 μM; 3 d, K i=3.81 μM). No inhibition was recorded against the bovine pancreatic α-chymotrypsin, which thus confirms the selectivity towards the target enzyme. Docking studies of 3 c and related inhibitors into the yeast proteasome revealed the structural basis for specificity. The evaluation of growth inhibitory effects against 60 human tumor cell lines was performed at the US National Cancer Institute. Among the selected compounds, 3 c showed 50 % growth inhibition (GI50) values at the sub-micromolar level on all cell lines.
- Scarbaci, Kety,Troiano, Valeria,Ettari, Roberta,Pinto, Andrea,Micale, Nicola,Di Giovanni, Carmen,Cerchia, Carmen,Schirmeister, Tanja,Novellino, Ettore,Lavecchia, Antonio,Zappalà, Maria,Grasso, Silvana
-
p. 1801 - 1816
(2014/08/18)
-
- Development of peptidomimetic boronates as proteasome inhibitors
-
Proteasome inhibition has emerged over the past decade as an effective therapeutic approach for the treatment of hematologic malignancies. It is a multicatalytic complex, whose proteolytic activity relies in three types of subunits: chymotrypsin-like (β5), trypsin-like (β2) and caspase-like (β1). Most important for the development of effective antitumor agents is the inhibition of the β5 subunits. In this context, the dipeptide boronate bortezomib (Velcade) represents the first proteasome inhibitor approved by the FDA and the lead compound in drug discovery. This paper describes the synthesis and biological evaluation of a series of conformationally constrained pseudopeptide boronates (1-3) structurally related to bortezomib. The synthesized compounds showed a promising inhibitory profile by blocking primarily the chymotrypsin-like activity of the proteasome with Ki values in submicromolar/micromolar range. These compounds also resulted quite selective since no significant inhibition was recorded in the test against bovine pancreatic α-chymotrypsin. The obtained results were rationalized by means of docking experiments based on a model of the crystal structure of bortezomib bound to the yeast 20S proteasome providing essential insights for further optimization of this class of inhibitors.
- Micale, Nicola,Ettari, Roberta,Lavecchia, Antonio,Di Giovanni, Carmen,Scarbaci, Kety,Troiano, Valeria,Grasso, Silvana,Novellino, Ettore,Schirmeister, Tanja,Zappalà, Maria
-
-
- Preparation of N-alkyl 2-pyridones via a lithium iodide promoted oto N-alkyl migration: Scope and mechanism
-
An efficient and inexpensive LiI-promoted O- to N-alkyl migration of 2-benzyloxy-, 2-allyloxy-, and 2-propargyloxypyridines and heterocycles is reported. The reaction produces the corresponding N-alkyl 2-pyridones and analogues under green, solvent-free conditions in good to excellent yields (30 examples, 20-97% yield). This method has been shown to be intermolecular and requires heat and lithium cation to occur.
- Tasker, Sarah Z.,Bosscher, Michael A.,Shandro, Christina A.,Ryu, Keun Ah,Snapper, Gregory S.,Utter, Jarrad M.,Anderson, Carolyn E.,Lanni, Erica L.,Ellsworth, Bruce A.
-
p. 8220 - 8230,11
(2020/10/15)
-
- New reagents for the synthesis of arylmethyl ethers and esters
-
This Account chronicles efforts leading up to the development of new arylmethyl transfer (benzylation) reagents for protecting oxygen functional groups under relatively mild and neutral conditions. It begins with an investigation of organosiletanes as surrogate hydroxyl groups, which inspired siletane-functionalized benzyl ethers and forced us to confront the difficulties associated with the synthesis of benzyl ethers. The end result is a new series of neutral oxypyridinium salts for the benzylation of various nucleophilic functional groups under mild conditions. 1 Introduction 2 Tamao-type Oxidation of Strained Organosiletanes 3 p-Siletanylbenzyl (PSB) Protecting Groups 4 2-Benzyloxy-1-methylpyridinium Triflate 5 Friedel-Crafts Reactions and Mechanistic Insights 6 Benzyl Ester Formation 7 Substituted Benzyl Transfer Reagents 8 Conclusions and Outlook. Georg Thieme Verlag Stuttgart New York.
- Albiniak, Philip A.,Dudley, Gregory B.
-
scheme or table
p. 841 - 851
(2010/07/10)
-
- Compounds and methods of arylmethylation (benzylation) as protection for alcohol groups during chemical synthesis
-
A process for benzylating an alcohol includes mixing 2-benzyloxy-1-methylpyridinium triflate in an aromatic hydrocarbon solvent having a predetermined boiling point; adding an acid scavenger to the mixture; combining the alcohol to be benzylated with the mixture; reacting the alcohol with the 2-benzyloxy-1-methylpyridinium triflate by heating above ambient temperature to generate the benzylated alcohol; and separating the benzylated alcohol from the mixture.
- -
-
Page/Page column 7; 8
(2010/07/14)
-
- Microwave-assisted silver(I)-mediated selective O-alkylation of aromatic imidate systems
-
A novel microwave-assisted protocol has been developed for the selective O-alkylation of aromatic imidate systems with various halides under microwave irradiation using silver carbonate as the base. Products were obtained in short reaction time and in excellent yields. Georg Thieme Verlag Stuttgart.
- Singh, Brajendra K.,Cavalluzzo, Claudia,De Maeyer, Marc,Debyser, Zeger,Parmar, Virinder S.,Van Der Eycken, Erik
-
experimental part
p. 2725 - 2728
(2010/01/21)
-
- [1,2]-Anionic rearrangement of 2-benzyloxypyridine and related pyridyl ethers
-
(Chemical Equation Presented) An anionic rearrangement of 2-benzyloxypyridine is described. Pyridine-directed metalation of the benzylic carbon leads to 1,2-migration of pyridine via a postulated associative mechanism (addition/elimination). Several aryl pyridyl carbinols were obtained in high yields. A formal synthesis of carbinoxamine, an antihistamine drug used for the treatment of seasonal allergies and hay fever, emerges from this methodology.
- Yang, Jingyue,Dudley, Gregory B.
-
supporting information; experimental part
p. 7998 - 8000
(2010/03/01)
-
- NOVEL PIPERAZINE DERIVATIVES AS INHIBITORS OF STEAROYL-CoA DESATURASE
-
The present invention relates to piperazine derivatives that act as inhibitors of stearoyl-CoA desaturase. The invention also relates to methods of preparing the compounds, compositions containing the compounds, and to methods of treatment using the compounds.
- -
-
Page/Page column 22
(2009/10/01)
-
- Alkylation of the 2-hydroxypyridine anion in ionic liquid media
-
The alkylation reaction of the ambident 2-hydroxypyridine anion was examined in ionic liquid media. Ionic liquids increase the alkylation reaction rate in comparison with molecular liquids, as well as the level of impact on the reaction rates of the count
- Vavilina,Zicmanis,Mekss,Klavins
-
p. 549 - 558
(2013/07/27)
-
- Synthesis of substituted N-benzyl pyridones via an O- To N-alkyl migration
-
(Chemical Equation Presented) A new LiI-promoted O- to N-alkyl migration has been developed for the conversion of O-alkylated 2-hydroxy pyridines, quinolines, and pyrimidines to the corresponding N-alkylated heterocycles in good to excellent yields (57-99%). This method serves as an efficient means for the preparation of N-benzyl pyridones, quinolones, and pyrimidones.
- Lanni, Erica L.,Bosscher, Michael A.,Ooms, Bartel D.,Shandro, Christina A.,Ellsworth, Bruce A.,Anderson, Carolyn E.
-
p. 6425 - 6428
(2008/12/21)
-
- Hydroxylamine O-benzyl ether as an ammonia equivalent in the catalytic amination of aryl halides
-
The palladium catalysed amination of aryl bromides with hydroxylamine O-benzyl ether leads to the formation of diaryl or triarylamines depending on the size of the aryl bromide, the number of equivalents used or the conditions employed.
- Bedford, Robin B.,Betham, Michael
-
p. 8947 - 8950
(2008/03/14)
-
- Mix-and-heat benzylation of alcohols using a bench-stable pyridinium salt
-
2-Benzyloxy-1-methylpyridinium inflate (1) is a stable, neutral organic salt that converts alcohols into benzyl ethers upon warming. The synthesis and reactivity of 1 are described herein. Benzylation of a wide range of alcohols occurs in good to excellent yield.
- Poon, Kevin W. C.,Dudley, Gregory B.
-
p. 3923 - 3927
(2007/10/03)
-
- Microwave-promoted synthesis of amino-substituted 2-pyridone derivatives via palladium-catalyzed amination reaction
-
A rapid and efficient synthesis of amino-substituted 2-pyridones was demonstrated by palladium-catalyzed amination reaction under microwave irradiation. This high-speed synthesis provided a number of amino-substituted 2-pyridones from the corresponding bromo-2-benzyloxypyridines via palladium-catalyzed amination followed by hydrogenolysis of benzyl ether.
- Heo, Jung-Nyoung,Young, Seob Song,Bum, Tae Kim
-
p. 4621 - 4625
(2007/10/03)
-
- A bench-stable organic salt for the benzylation of alcohols
-
2-Benzyloxy-1-methylpyridinium inflate (Bn-OPT) effects the benzylation of alcohols in the absence of acidic or basic promoters. Solutions of Bn-OPT and primary, secondary, or tertiary alcohols give rise to the corresponding benzyl ethers upon mild heating. Acid scavengers are generally included in the reaction mixture. Bn-OPT is crystalline and bench-stable. Georg Thieme Verlag Stuttgart.
- Poon, Kevin W. C.,House, Sarah E.,Dudley, Gregory B.
-
p. 3142 - 3144
(2007/10/03)
-
- Synthesis of substituted pyridines by the reactions of halopyridines with sulfur, oxygen and carbon nucleophiles under focused microwave irradiation
-
The nucleophilic substitution reactions of halopyridines with sulfur, oxygen and carbon nucleophiles under microwave irradiation was complete within several minutes with yields up to 99%. The method using microwave irradiation is superior to those conducted under conventional heating processes.
- Cherng, Yie-Jia
-
p. 4931 - 4935
(2007/10/03)
-
- N- vs. O-alkylation in the Mitsunobu reaction of 2-pyridone
-
An N- vs. O-alkylation study of 2-pyridone with various alcohols and solvents under Mitsunobu conditions was carried out.
- Comins, Daniel L.,Jianhua, Gao
-
p. 2819 - 2822
(2007/10/02)
-
- Selective alkylation of 2-pyridone in solvent-free conditions
-
Alkylation of 2-pyridone has been performed in solvent-free conditions. The effect of base, phase transfer agent, and alkylation agent has been discussed.
- Almena,Diez-Barra,de la Hoz
-
p. 1057 - 1063
(2007/10/02)
-
- EASY AND EFFICIENT SNAr REACTIONS ON HALOPYRIDINES IN SOLVENT FREE CONDITIONS
-
Solid-liquid phase transfer catalysis (PTC) without added solvent efficiently promotes SNAr reactions on halopyridines with a variety of anionic nucleophiles generated in situ.This metodology gives access to substituted pyridines in very simplified conditions depending on halide nature.Mechanistic investigations are proposed.
- Loupy, Andre,Philippon, Noelle,Pigeon, Phillippe,Galons, Herve
-
p. 1947 - 1953
(2007/10/02)
-
- STUDY OF THE CATALYTIC PROPERTIES OF TRIS (3,6-DIOXAHEPTYL)AMINE (TDA-1) IN HETEROAROMATIC NUCLEOPHILIC SUBSTITUTION OF CHLOROPYRIDINES AND THEIR N-OXIDES
-
Catalytic properties of tris(3,6-dioxaheptyl)amine (TDA-1) have been analyzed in reactions of alkoxydehalogenation of 2- and 4-chloropyridine and their N-oxides under solid-liquid phase transfer catalysis conditions.Alkoxypyridines were obtained in excellent yields but with N-oxides a competitive alkaline cleavage of the performed ether was observed.
- Ballesteros, P.,Claramunt, R.M.
-
p. 2557 - 2564
(2007/10/02)
-
- ALKYLATION OF 2-HYDROXYBENZOTHIAZOLE SALTS
-
The alkylation reactions of 2-hydroxybenzothiazole salts with various alkyl halides afford the N-alkylated derivatives.With alkyl halides prone to molecular reactions, 2-hydroxybenzothiazole in the presence of silver carbonate, yields N- and O-alkylated p
- Collina, Gianni,Forlani, Luciano,Mezzina, Elisabetta,Sintoni, Marina,Todesco, Paolo E.
-
p. 281 - 286
(2007/10/02)
-
- Kinetics of Benzylation of Hydroxypyridines & Hydroxyquinolines in Dimethyl Sulphoxide - Water & Isopropanol - Water Mixtures
-
The kinetics of benzylation of hydroxypyridines and hydroxyquinolines have been investigated in DMSO-water and isopropanol-water mixtures.A formal comparison of rate of benzylation of phenols and naphthols has also been made.DMSO, being a dipolar aprotic solvent facilitates O-alkylation of phenols and naphthols and a considerable rate increase has been observed in DMSO-water, giving the O-alkylated products in more than 90percent yield in both the cases.However, in the case of benzylation of hydroxypyridine in DMSO-water, O-alkylated product formed is only 65percent and the magnitude of rate increase, compared to phenols and naphthols, is much less, under similar conditions.But the rate of benzylation of 8-hydroxyquinoline in DMSO-water is retarded considerably and the rate is even slower than the rate of N-benzylation of quinoline, indicating only O-benzylation of 8-hydroxyquinoline in DMSO-water is unique and is mainly due to greater ground state solvation of substrate by DMSO, a factor which has been considered insignificant in all the other cases.
- Rajasekar, N.,Srinivasan, V. S.,Venkatasubramanian, N.
-
p. 800 - 802
(2007/10/02)
-