- Oxidation of N-acyl-pyrrolidines to imides with CrO3·3,5- dimethylpyrazole
-
N-Acyl-pyrrolidones are easily obtained by treatment of N-acyl- pyrrolidines with CrO33,5-dimethylpyrazole complex (CrO33,5-DMP) at room temperature.
- Blay, Gonzalo,Cardona, Luz,Garcia, Begona,Garcia, Cristina L.,Pedro, Jose R.
-
-
Read Online
- Zirconium-catalysed N-acylation of lactams using unactivated carboxylic acids
-
A large number of chemicals including surfactants, nootropic drugs and pesticides contain an N-acylated lactam moiety in their molecular structure. In this work, the direct, catalytic N-acylation of a number of lactams with various unactivated carboxylic
- Hulsbosch, Joris,Claes, Laurens,De Vos, Dirk E.
-
-
Read Online
- Evaluation of Cyclic Amides as Activating Groups in N-C Bond Cross-Coupling: Discovery of N-Acyl-δ-valerolactams as Effective Twisted Amide Precursors for Cross-Coupling Reactions
-
The development of efficient methods for facilitating N-C(O) bond activation in amides is an important objective in organic synthesis that permits the manipulation of the traditionally unreactive amide bonds. Herein, we report a comparative evaluation of a series of cyclic amides as activating groups in amide N-C(O) bond cross-coupling. Evaluation of N-acyl-imides, N-acyl-lactams, and N-acyl-oxazolidinones bearing five- and six-membered rings using Pd(II)-NHC and Pd-phosphine systems reveals the relative reactivity order of N-activating groups in Suzuki-Miyaura cross-coupling. The reactivity of activated phenolic esters and thioesters is evaluated for comparison in O-C(O) and S-C(O) cross-coupling under the same reaction conditions. Most notably, the study reveals N-acyl-δ-valerolactams as a highly effective class of mono-N-acyl-activated amide precursors in cross-coupling. The X-ray structure of the model N-acyl-δ-valerolactam is characterized by an additive Winkler-Dunitz distortion parameter ?(τ+χN) of 54.0°, placing this amide in a medium distortion range of twisted amides. Computational studies provide insight into the structural and energetic parameters of the amide bond, including amidic resonance, N/O-protonation aptitude, and the rotational barrier around the N-C(O) axis. This class of N-acyl-lactams will be a valuable addition to the growing portfolio of amide electrophiles for cross-coupling reactions by acyl-metal intermediates.
- Bisz, Elwira,Chen, Hao,Dziuk, B?a?ej,Ejsmont, Krzysztof,Lalancette, Roger,Pyle, Daniel J.,Rahman, Md. Mahbubur,Szostak, Michal,Szostak, Roman,Wang, Qi
-
p. 10455 - 10466
(2021/07/31)
-
- Carbazole-containing amides and ureas: Discovery of cryptochrome modulators as antihyperglycemic agents
-
A series of novel carbazole-containing amides and ureas were synthesized. A structure–activity relationship study of these compounds led to the identification of potent cryptochrome modulators. Based on the desired pharmacokinetic/pharmacodynamic parameters and the results of efficacy studies in db/db mice, compound 50 was selected for further profiling.
- Humphries, Paul S.,Bersot, Ross,Kincaid, John,Mabery, Eric,McCluskie, Kerryn,Park, Timothy,Renner, Travis,Riegler, Erin,Steinfeld, Tod,Turtle, Eric D.,Wei, Zhi-Liang,Willis, Erik
-
supporting information
p. 293 - 297
(2018/01/04)
-
- CuCl/TMEDA/nor-AZADO-catalyzed aerobic oxidative acylation of amides with alcohols to produce imides
-
Although aerobic oxidative acylation of amides with alcohols would be a good complement to classical synthetic methods for imides (e.g., acylation of amides with activated forms of carboxylic acids), to date, there have been no reports on oxidative acylation to produce imides. In this study, we successfully developed, for the first time, an efficient method for the synthesis of imides through aerobic oxidative acylation of amides with alcohols by employing a CuCl/TMEDA/nor-AZADO catalyst system (TMEDA = teramethylethylendiamine; nor-AZADO = 9-azanoradamantane N-oxyl). The proposed acylation proceeds through the following sequential reactions: aerobic oxidation of alcohols to aldehydes, nucleophilic addition of amides to the aldehydes to form hemiamidal intermediates, and aerobic oxidation of the hemiamidal intermediates to give the corresponding imides. This catalytic system utilizes O2 as the terminal oxidant and produces water as the sole by-product. An important point for realizing this efficient acylation system is the utilization of a TMEDA ligand, which, to the best of our knowledge, has not been employed in previously reported Cu/ligand/N-oxyl systems. Based on experimental evidence, we consider that plausible roles of TMEDA involve the promotion of both hemiamidal oxidation and regeneration of an active CuII-OH species from a CuI species. Here promotion of hemiamidal oxidation is particularly important. Employing the proposed system, various types of structurally diverse imides could be synthesized from various combinations of alcohols and amides, and gram-scale acylation was also successful. In addition, the proposed system was further applicable to the synthesis of α-ketocarbonyl compounds (i.e., α-ketoimides, α-ketoamides, and α-ketoesters) from 1,2-diols and nucleophiles (i.e., amides, amines, and alcohols).
- Kataoka, Kengo,Wachi, Keiju,Jin, Xiongjie,Suzuki, Kosuke,Sasano, Yusuke,Iwabuchi, Yoshiharu,Hasegawa, Jun-Ya,Mizuno, Noritaka,Yamaguchi, Kazuya
-
p. 4756 - 4768
(2018/06/07)
-
- CARBAZOLE-CONTAINING AMIDES, CARBAMATES, AND UREAS AS CRYPTOCHROME MODULATORS
-
The subject matter herein is directed to carbazole-containing amide, carbamate, and urea derivatives and pharmaceutically acceptable salts or hydrates thereof of structural formula I wherein the variable R1, R2, R3, R4, R5, R6, R7, A, D, E, G, J, L, M, Q, a, and b are accordingly described. Also provided are pharmaceutical compositions containing the compounds of formula I to treat a Cry-mediated disease or disorder, such as diabetes, complications associated with diabetes, Cushing's syndrome, NASH, NAFLD, asthma, and COPD.
- -
-
Paragraph 0275
(2015/10/28)
-
- Laccase/2,2,6,6-tetramethylpiperidinoxyl radical (TEMPO): An efficient catalytic system for selective oxidations of primary hydroxy and amino groups in aqueous and biphasic media
-
Copper salts/2,2,6,6-tetramethylpiperidinoxyl radical (TEMPO) catalytic systems enable efficient aerobic oxidations of primary alcohols but they generally show a reduced reactivity in aqueous medium. Herein, we report an oxidative catalytic system composed of Trametes versicolor laccase and TEMPO, which is able to work in buffer solutions at room temperature using ambient air. Although this catalytic system displays great efficiency in aqueous systems, the addition of methyl tert-butyl ether allows the reduction of TEMPO loading, also enhancing the solubility of hydrophobic compounds. This practical methodology promotes the chemoselective aerobic oxidation of hydroxy or amino groups, leading to interesting organic derivatives such as aldehydes, lactones, hemiaminals or lactams.
- Díaz-Rodríguez, Alba,Martínez-Montero, Lía,Lavandera, Iván,Gotor, Vicente,Gotor-Fernández, Vicente
-
supporting information
p. 2321 - 2329
(2014/07/21)
-
- Synthesis of imides and benzoylureas by direct oxidation of N-methylenes of amides and benzylureas
-
Some amides and benzylureas can be oxidised to imides and benzoylureas, respectively, using silver(I) nitrate (20 mol %), copper(II) sulfate pentahydrate (20 mol %), ammonium persulfate (3.0 equiv.), and potassium fluoride (20 equiv.) in water at room temperature.
- Huang, Wenhua,Xu, Mei-Li
-
-
- Direct N-acylation of lactams, oxazolidinones, and imidazolidinones with aldehydes by Shvo's catalyst
-
Direct N-acylation of lactams, oxazolidinones, and imidazolidinones was achieved with aldehydes by Shvo's catalyst without using any other stoichiometric reagent. The N-acylations with α,β-unsaturated aldehydes were achieved with excellent yields.
- Zhang, Jian,Hong, Soon Hyeok
-
supporting information
p. 4646 - 4649
(2012/10/29)
-
- DIARYLMETHYLAMIDE DERIVATIVE HAVING ANTAGONISTIC ACTIVITY ON MELANIN-CONCENTRATING HORMONE RECEPTOR
-
[Problem] To provide a melanin-concentrating hormone receptor antagonist useful as a pharmaceutical agent for central diseases, circulatory diseases, and metabolic diseases. [Means for Resolution] Provided is a diarylmethylamide derivative represented by
- -
-
Page/Page column 44-45
(2011/02/17)
-
- Conversion of N-Acyl amino acids into imides via oxidative decarboxylation induced by Ag+/Cu2+/S2O8 2- in water
-
N-Acyl amino acids can be converted by oxidative decarboxylation induced by Ag+/Cu2+/S2O82- at room temperature in water into imides in 24-89% yields. Both N-benzoylvaline and N-benzoylleucine gave N-
- Huang, Wenhua,Wang, Meiling,Yue, Hong
-
p. 1342 - 1344
(2008/12/21)
-
- Ruthenium tetroxide oxidation of cyclic N-acylamines by a single layer method: formation of ω-amino acids
-
The ruthenium tetroxide oxidation of cyclic N-acyl amines by a 10% NaIO4 aqueous solution containing tert-butanol as a single layer system resulted in the endo-cyclic C-N bond cleavage to afford the ω-amino acids as almost sole products in good yields, while a similar oxidation under the double layer using a NaIO4 aqueous solution, and ethyl acetate gave the N-acyl lactams.
- Kaname, Mamoru,Yoshifuji, Shigeyuki,Sashida, Haruki
-
p. 2786 - 2788
(2008/09/19)
-
- A simple synthesis of 4-(2-aminoethyl)-5-hydroxy-1H-pyrazoles
-
A simple four-step synthesis of 4-(2-aminoethyl)-5-hydroxy-1H-pyrazoles 8 (or their 1H-pyrazol-3(2H)-one tautomers 8′) as the pyrazole analogues of histamine was developed. First, enamino lactam 3 was prepared as the key intermediate in two steps from 2-p
- Kralj, David,Gro?elj, Uro?,Meden, Anton,Dahmann, Georg,Stanovnik, Branko,Svete, Jurij
-
p. 11213 - 11222
(2008/02/12)
-
- Unique oxidation reaction of amides with pyridine-N-oxide catalyzed by ruthenium porphyrin: Direct oxidative conversion of N-acyl-L-proline to N-acyl-L-glutamate
-
Oxidations of alkanes, alkenes, and aromatic rings with pyridine N-oxides are efficiently catalyzed by ruthenium porphyrins under mild conditions. We show here that the oxidation of N-acyl cyclic amines with RuIVtetraarylporphyrin dichloride-2,6-substituted pyridine N-oxides directly gives N-acyl amino acids in modest to good yield via oxidative C-N bond cleavage. N-Acylpyrrolidines and N-acylpiperidines were converted to N-acyl-γ-aminobutyric acids and N-acyl-δ-aminovaleric acids, respectively. This type of reaction is a novel one in which the C-N bond is cleaved selectively at the less substituted carbon. Notably, the proline residue in proline-containing peptides was selectively converted to glutamate. A large intramolecular kinetic isotope effect (kH/kD = 9.8) was observed in the oxidation of N-benzoyl[2,2,-d2]pyrrolidine, indicating that the reaction should involve an α-hydrogen atom abstraction process as the rate-determining step. N-Acylcarbaldehyde, the putative intermediate ring-opened form of α-hydroxylated N-acyl cyclic amine, was readily oxidized with the oxidizing system to afford the corresponding N-acylamino acid in good yield. Further, lactams (1-methyl-2-pyrrolidone and 1-methyl- 2-piperidone) were also oxidized to give the corresponding imides (1-methylsuccinimide and 1-methylpiperidine-2,6-dione). Copyright
- Ito, Rina,Umezawa, Naoki,Higuchi, Tsunehiko
-
p. 834 - 835
(2007/10/03)
-
- A bromine-catalysed free-radical oxidation of acetamides from primary and secondary alkylamines by H2O2
-
New procedures based on the oxidation by bromine-catalysed hydrogen peroxide in a two-phase system provide simple and cheap transformations of alkylamines to carbonyl derivatives (aldehydes, ketones, carboxylic acid, imides, lactams) through the corresponding acetamides.
- Bjorsvik,Fontana,Liguori,Minisci
-
p. 523 - 524
(2007/10/03)
-
- Heck reactions without salt formation: Aromatic carboxylic anhydrides as arylating agents
-
Environmentally benign and economical production of arylated olefins can be achieved by a new variant of the Heck reaction in which no halogen salts are formed. The trick is the use of aromatic carboxylic anhydrides 1 as arylating agents. With halide-activated palladium chloride as catalyst, which requires no phosphane ligands, the olefins 2 can be prepared according to Equation (a) in good yields.
- Stephan, Massoud S.,Teunissen, Antonius J. J. M.,Verzijl, Gerard K. M.,De Vries, Johannes G.
-
p. 662 - 664
(2007/10/03)
-
- Autoxidation of intermediary mesoionic 1,3-oxazolium-5-olates generated from cyclic N-acyl α-amino acids
-
Mesoionic 1,3-oxazolium-5-olates (munchnones) react fairly rapidly with oxygen to give the autoxidation products when the C-4 substituent is aromatic. The autoxidation occurred in the munchnones generated from N-acyl tetrahydroisoquinoline-1-carboxylic ac
- Kawase, Masami
-
p. 1248 - 1253
(2007/10/03)
-
- NEW CONDENSING REAGENTS: THIOPHOSPHORUS COMPOUNDS ACTIVATED BY 2-OXAZOLONE AND 2-BENZOXAZOLINONE HETEROCYCLES
-
The thiophosphorus compounds (3-6) activated by 2-oxazolone and 2-benzoxazolinone heterocycles, which have the advantages of high solubility in organic solvents and good preservability, serve well as versatile condensing reagents for one-step formation of amides including β-lactams, esters and thioesters from carboxylic acids.
- Otsubo, Teruyuki,Matsukawa, Chiyoko,Ishizuka, Tadao,Kunieda, Takehisa
-
p. 131 - 134
(2007/10/02)
-
- Synthesis and anticonvulsant activity of 1-acyl-2-pyrrolidinone derivatives
-
Several 1-acyl-2-pyrrolidinone derivatives were synthesized as derivatives of γ-aminobutyric acid (GABA), and their pharmacological activities and stabilities were investigated. The derivatives showed anticonvulsant effect on picrotoxin-induced seizure at a dose of 200 mg/kg. In particular, 1-decanoyl-2-pyrrolidinone (7) and 1-dodecanoyl-2-pyrrolidinone (8) had a high activity. The anticonvulsant activity showed a dose dependency. Some of 1-acyl-2-pyrrolidinone derivatives prolonged sleeping time which was induced by sodium pentobarbital and showed a recovery from disruption of the memory of passive avoidance response, which was induced by an electroconvulsive shock. As shown by the results of the stability study of 1-acetyl-2-pyrrolidinone (1), it was degraded in an acidic buffer and an alkaline buffer although 2-pyrrolidinone was stable. 1-Acyl-2-pyrrolidinone derivatives were degraded in liver and brain homogenates of mouse and rat. They showed a degradation rate in rat plasma. Conversion of 8 to GABA in mouse liver homogenate was demonstrated. These results suggested that the pharmacological activity of 1-acyl-2-pyrrolidinone is probably due to the release of GABA by hydrolysis of derivatives although further work is necessary.
- Sasaki,Mori,Nakamura,Shibasaki
-
p. 628 - 633
(2007/10/02)
-
- Organometallic Ring-Opening Reactions of N-Acyl and N-Alkoxycarbonyl Lactams. Synthesis of Cyclic Imines
-
The reactions of hexyl- and phenylmagnesium bromides with N-acyl and N-alkoxycarbonyl lactams in tetrahydrofuran at -78 deg C have been performed to determine the factors affecting the regioselectivity.N-Pivaloyl γ- and δ-lactams undergo the ring-opening reactions with both Grignard reagents, whereas on the N-benzoyl γ-lactam a complete selectivity is achieved only with phenylmagnesium bromide.The N-Cbz γ- and δ-lactams preferentially react at the exocyclic carbonyl group, especially with hexylmagnesium bromide.The N-Boc five- to eight-membered lactams undergo the ring-opening reaction to give N-Boc-ω-amino ketones, although the efficiency slightly decreases by increasing the ring size.The deprotection of the N-Boc-ω-amino ketones with trifluoroacetic acid easily affords the corresponding five- to seven-membered cyclic imines.Pyridine alkaloids containing the cyclic imine moiety have been prepared by a modified route, exploiting the more easily available pyridyllithium reagents, instead of the corresponding Grignard reagents.
- Giovannini, Arianna,Savoia, Diego,Umani-Ronchi, Achille
-
p. 228 - 234
(2007/10/02)
-
- Hydroxylations microbiologiques de pyrrolidinones-2 (note de laboratoire)
-
Microbial hydroxylations of various pyrrolidin-2 ones, especially N-acylated, with Beauveria sulfurescens have been carried out.The regioselectivity depends on the nature of the substituent on the nitrogen atom and the hydroxylation may occur at position 3,4 or 5 of the heterocycle.Hydroxylations at position 3 or 4 occur with low enantioselectivity.
- Srairi, Driss,Maurey, Georges
-
p. 297 - 301
(2007/10/02)
-
- Oxidation of N-Acyl-Pyrrolidines and -Piperidines with Iron(II)-Hydrogen Peroxide and an Iron Complex-Molecular Oxygen
-
The reactions of N-acyl-pyrrolidines (1a-c) and -piperidines (1d-f) with Fe(II)-hydrogen peroxide in aqueous 95percent acetonitrile gave the corresponding pyrrolidin-2-ones (2a-c) and piperidin-2-ones (2d-f).The lactams (2a-f) were also the products in the oxidation of (1a-f) with molecular oxygen in the presence of an iron complex, either or , in aqueous 90percent pyridine.
- Murata, Satoru,Miura, Masahiro,Nomura, Masakatsu
-
p. 1259 - 1262
(2007/10/02)
-
- Anodic Oxidation of Amides and Lactams Using N-Hydroxyphthalimide as a Mediator
-
Indirect electrochemical oxidation of amides and N-alkyllactams was performed using N-hydroxyphthalimide as a mediator.A carbonyl group was introduced in good yield at the α-carbon to the nitrogen of the compounds.Keywords - anodic oxidation; mediator; amide; N-alkyllactam; N-hydroxyphthalimide; imide; N-acyllactam; glassy-carbon electrode
- Masui, Masaichiro,Hara, Seijiro,Ozaki, Shigeko
-
p. 975 - 979
(2007/10/02)
-