cas 67442-07-3, 2-CHLORO-N-METHOXY-N-METHYLACETAMIDE

Articles about 67442-07-3Total 38 be found

Article title
Article abstract
Author
Journal number and time
Download

Substituted Tetraethynylethylene–Tetravinylethylene Hybrids
A general synthetic approach to molecular structures that are hybrids of tetraethynylethylene (TEE) and tetravinylethylene (TVE) is reported. The synthesis permits the controlled preparation of many previously inaccessible structures, including examples w
Connor, Kieran P. E.,Horvath, Kelsey L.,Magann, Nicholas L.,Sherburn, Michael S.,Sowden, Madison J.,Westley, Erin
supporting information
p. 977 - 986
(2022/02/03)

Development of a practical synthesis to PI3K α-selective inhibitor GDC-0326
A practical route to PI3K α-selective inhibitor GDC-0326 is reported. The synthesis leverages an existing scheme to a key tetracyclic benzoxazepine intermediate and optimizes it for robustness and scalability, including removing numerous undesired conditions and reagents, as well as eliminating chromatographic purification steps. The process endgame is streamlined to utilize a single-step, stereocontrolled alkylation of the key phenol with a chiral lactamide mesylate, followed by recrystallization of the lactamide ether product, to deliver the desired enantiomer of the active pharmaceutical ingredient (API) GDC-0326.
Koenig, Stefan G.,Green, Keena L.,Müller, Barbara,Sowell, C. Gregory,Askin, David,Gosselin, Francis
(2020/12/29)

Concise and Efficient Synthesis of [6]-Paradol
An efficient synthesis of [6]-paradol (1) has been performed in four steps with a 72.0% overall yield. The present method highlights commercially available materials, convenient isolation with multiple crystallization without involving column chromatography, and a high-purity product (more than 99.2%), and it is amenable to large-scale synthesis.
Shi, Xiang,Xia, Tiantian,McKamey, Brooke E.,Wu, Xian,Sun, Yue,Zhou, Weifeng,Zhang, Guangyan
p. 1360 - 1365
(2021/06/21)

3-SUBSTITUTED PHENYLAMIDINE COMPOUNDS, PREPARATION AND USE THEREOF
The present invention discloses 3 - substituted anilino compounds of formula (I) in which R 1, R 2, R 3, R 4, R 44a, R 44b, A and E are as defined in the description. The present invention further discloses processes for preparing compounds of general formula (I) and using compounds of general formula (I) as crop protection agents for agricultural crops.
-
Paragraph 0389-0390

(2021/10/14)

Quaternary Charge-Transfer Complex Enables Photoenzymatic Intermolecular Hydroalkylation of Olefins
Intermolecular C-C bond-forming reactions are underdeveloped transformations in the field of biocatalysis. Here we report a photoenzymatic intermolecular hydroalkylation of olefins catalyzed by flavin-dependent 'ene'-reductases. Radical initiation occurs via photoexcitation of a rare high-order enzyme-templated charge-transfer complex that forms between an alkene, α-chloroamide, and flavin hydroquinone. This unique mechanism ensures that radical formation only occurs when both substrates are present within the protein active site. This active site can control the radical terminating hydrogen atom transfer, enabling the synthesis of enantioenriched γ-stereogenic amides. This work highlights the potential for photoenzymatic catalysis to enable new biocatalytic transformations via previously unknown electron transfer mechanisms.
Page, Claire G.,Cooper, Simon J.,Dehovitz, Jacob S.,Oblinsky, Daniel G.,Biegasiewicz, Kyle F.,Antropow, Alyssa H.,Armbrust, Kurt W.,Ellis, J. Michael,Hamann, Lawrence G.,Horn, Evan J.,Oberg, Kevin M.,Scholes, Gregory D.,Hyster, Todd K.
supporting information
p. 97 - 102
(2021/01/12)

Paradol synthesis method
The invention discloses a complete synthesis method of a natural product paradol, the route being represented as the specification. The method employs feasible raw materials and simple operation, is high in yield and low in cost, is high in final product purity, is controllable in quality, and is suitable for industrial production.
-
Paragraph 0032; 0038

(2020/04/17)

PESTICIDAL MIXTURES COMPRISING A MESOIONIC COMPOUND
Pesticidal mixtures comprising as active compounds 1) pesticidally active compound A of formula (I) and 2) at least one further compound B selected from compounds B1 to B22 as described in claims and the description.
-
Page/Page column 48; 51; 52

(2020/04/25)

PYRIMIDINIUM COMPOUNDS AND THEIR MIXTURES FOR COMBATING ANIMAL PESTS
The present invention relates to pyrimidinium compounds of formula (I), to the stereoisomers, salts, tautomers and N-oxides thereof, their mixtures and to compositions comprising such compounds or mixtures. The invention also relates to methods and uses o
-
Paragraph 0386; 0403

(2020/07/31)

METHOD OF CONTROLLING RICE PESTS IN RICE
The present invention relates to methods for controlling rice pest invertebrates, which methods comprise applying pyrimidinium compounds of formula (I), the stereoisomers, salts, tautomers and N-oxides thereof, their mixtures and compositions comprising such compounds or mixtures, by seedling box application.
-
Paragraph 0154; 0155

(2020/09/22)

PROCESS FOR PREPARING S-CONTAINING PYRIMIDINIUM COMPOUNDS
The present invention relates to a process for preparing optically active compounds of formula X and intermediates thereof, wherein the variables of compound of formula X are as defined in the claims and the description.
-
Paragraph 0318-0319

(2020/08/18)

Multikilogram Synthesis of a Potent Dual Bcl-2/Bcl-xL Antagonist. 2. Manufacture of the 1,3-Diamine Moiety and Improvement of the Final Coupling Reaction
This paper describes the synthesis of kilogram quantities of the sulfonamide moiety 3 involved in a coupling reaction with acid moiety 2 to provide batches of drug candidate 1 for preclinical studies and first-in-human clinical trials. A first approach relying on a chiral separation furnished the desired enantiomer of 1,3-diamine 20, precursor of sulfonamide 3. An enantiomeric synthesis of 20 using the Ellman's chiral auxiliary coupled with an aza-Reformatsky reaction to control the stereochemistry is also discussed. Coupling conditions of the final step involving EDCI to provide 1 under a cGMP process are detailed. An alternative approach using N-(1-methanesulfonyl)benzotriazole is also presented.
Hardouin, Christophe,Baillard, Sandrine,Barière, Fran?ois,Craquelin, Anthony,Grandjean, Mathieu,Janvier, Solenn,Le Roux, Stéphane,Penloup, Christine,Russo, Olivier
p. 670 - 685
(2019/12/24)

3-SUBSTITUTED PHENYLAMIDINE COMPOUNDS, PREPARATION AND USE THEREOF
The present invention disclosed 3-substituted phenylamidine compounds of general formula (I), wherein R1, R2, R3, R4, R4a, R4b, A and E have the same meanings as defined in description. The
-
Page/Page column 93

(2020/07/31)

Manufacture of the PI3K β-Sparing Inhibitor Taselisib. Part 1: Early-Stage Development Routes to the Bromobenzoxazepine Core
Two convergent regioselective routes for the synthesis of the tetracyclic imidazobenzoxazepine triazole 1, a key intermediate toward the synthesis of taselisib, are described. In the first-generation route, a chemoselective Negishi cross-coupling reaction was developed between iodoimidazole 3 and triazole 7, which enabled the delivery of initial kilogram quantities of 1. Because of the inefficiencies in the preparation of the imidazole 3, a second-generation route via a highly regioselective imidazole ring formation between α-chloroketone 11 and aryl amidine 12 was developed. The resulting imidazole 14 provided the handle to efficiently install the seven-membered benzoxazepine ring system in one pot with two-step N-alkylation and SNAr tandem reactions.
Remarchuk, Travis,Angelaud, Rémy,Askin, David,Kumar, Archana,Thompson, Andrew S.,Cheng, Hua,Reichwein, John F.,Chen, Yanping,St-Jean, Frédéric
p. 775 - 782
(2019/05/24)

PROCESS FOR PREPARING CHIRAL 2,3-DIHYDROTHIAZOLO[3,2-A]PYRIMIDIN-4-IUM COMPOUNDS
The present invention relates to pyrimidinium compounds of formula (I), to the stereoisomers, salts, tautomers and N-oxides thereof, their mixtures and to compositions comprising such compounds or mixtures. The invention also relates to methods and uses o
-
Page/Page column 70; 73

(2018/10/25)

Enantiospecific Total Synthesis of (+)-3-epi-Epohelmin A Using a Nitrogen-Substituted Donor–Acceptor Cyclopropane
The enantiospecific total synthesis of (+)-3-epi-epohelmin was accomplished by rapid construction of the pyrrolizidine core starting from enantiopure l-pyrroglutamic acid. The key reaction included a highly regio- and stereoselective intramolecular cyclopropanation reaction, regioselective ring opening of a nitrogen-substituted donor–acceptor cyclopropane, stereoselective reduction of a ketone, chemoselective organolithium addition to a Weinreb amide, and chemoselective oxidation of an allylic alcohol.
Gharpure, Santosh J.,Nanda, Laxmi Narayan,Kumari, Dimple
supporting information
p. 3917 - 3920
(2017/07/28)

Stereospecific Decarboxylative Nazarov Cyclization Mediated by Carbon Dioxide for the Preparation of Highly Substituted 2-Cyclopentenones
Highly substituted 2-cyclopentenones were stereospecifically and regioselectively constructed with high catalytic efficiency through Lewis-acid catalyzed decarboxylative Nazarov cyclization of the cyclic carbonate derivative, which is prepared by reacting the propargyl alcohol with carbon dioxide in the presence of a silver catalyst. The stereochemistry of the 2-cyclopentenone is strictly controlled by the geometry of the alkene in the starting material. This method is applicable for various substrates.
Komatsuki, Keiichi,Sadamitsu, Yuta,Sekine, Kohei,Saito, Kodai,Yamada, Tohru
supporting information
p. 11594 - 11598
(2017/09/11)

TRICYCLIC PIPERAZINE DERIVATIVE
Disclosed are compounds useful as inhibitors of Phosphodiesterase 1 (PDE1), compositions thereof, and methods of using the same.
-
Paragraph 0595

(2016/04/19)

Direct Catalytic Asymmetric Aldol Reaction of an α-Azido Amide
A direct aldol reaction of an α-azido 7-azaindolinylamide, promoted by a Cu-based cooperative catalyst, is documented. Aromatic aldehydes bearing an ortho substituent exhibited diastereodivergency depending on the nature of the chiral ligands used. Smooth reactions with ynals highlighted the broad substrate scope. A vicinal azido alcohol unit in the product allowed direct access to the corresponding aziridine and facile hydrolysis of the 7-azaindolinylamide moiety furnished enantioenriched β-hydroxy-α-azido carboxylic acid derivatives.
Weidner, Karin,Sun, Zhongdong,Kumagai, Naoya,Shibasaki, Masakatsu
supporting information
p. 6236 - 6240
(2015/05/20)

Chemo-, regio-, and stereo-selective perfluoroalkylations by a Grignard complex with zirconocene
The synthesis of highly reactive perfluoroalkyl Grignard reagents with early transition metal zirconocene complexes and their new types of highly chemo-, regio-, and stereo-selective perfluoroalkylation reactions are reported with epoxides in particular. The zirconocene complex is advantageous in activating the perfluoroalkyl Grignard species. The zirconocene·Grignard complexes were clarified by DOSY. Both 1H and 19F DOSY analyses show that the addition of MAO and dioxane to the mixture of RFMgCl and Cp2ZrCl2 connects Cp2Zr and RFMg to generate the zirconocene/perfluoroalkyl-Grignard/dioxane complex.
Fujiu, Motohiro,Negishi, Kazuyuki,Guang, Jie,Williard, Paul G.,Kuroki, Shigeki,Mikami, Koichi
supporting information
p. 19464 - 19468
(2015/11/27)

Visible light photoredox-catalysed intermolecular radical addition of α-halo amides to olefins
We present α-chloro amides as a new class of α-acetyl radical precursors, which undergo a tin-free, photoredox-catalysed intermolecular α-alkylation with various olefins exclusively in an anti-Markovnikov fashion. The reaction represents a reductive atom
Nakajima, Masaki,Lefebvre, Quentin,Rueping, Magnus
supporting information
p. 3619 - 3622
(2014/04/03)

PROCESS FOR MAKING BENZOXAZEPIN COMPOUNDS
Processes are described for the preparation of PI3K inhibitor, GDC-0032, Formula (I), having the structure: Formula (I) (GDC-0032), and intermediates useful for the preparation of (I).
-
Page/Page column 10; 25

(2014/09/29)

COMPOUNDS AND PHARMACEUTICAL COMPOSITIONS THEREOF FOR THE TREATMENT OF INFLAMMATORY DISORDERS
The present invention discloses compounds according to Formula I: Wherein R1a, R1b, R2, R4, R5, R6a, R6b, R7, R8, W, X, Cy, and the subscript a are as defined herein. The present invention relates to compounds inhibiting autotaxin (NPP2 or ENPP2), methods for their production, pharmaceutical compositions comprising the same, and methods of treatment using the same, for the prophylaxis and/or treatment of diseases involving fibrotic diseases, proliferative diseases, inflammatory diseases, autoimmune diseases, respiratory diseases, cardiovascular diseases, neurodegenerative diseases, dermatological disorders, and/or abnormal angiogenesis associated diseasesby administering the compound of the invention.
-
Paragraph 00444-00445

(2014/09/29)

One-pot transition-metal-free synthesis of weinreb amides directly from carboxylic acids
Weinreb amides were prepared directly from carboxylic acids, N,O-dimethylhydroxylamine, and phosphorus trichloride in one pot at 60 °C in toluene in high yields, thus avoiding the separation of the moisture and air sensitive intermediate P[NMe(OMe)]3 in advance. Sterically hindered carboxylic acids also give the corresponding Weinreb amides in excellent yields. Various functional groups are tolerated on the carboxylic acid. The method, which is a simple process and gives high yields, is suitable for large-scale production. Georg Thieme Verlag KG Stuttgart · New York.
Niu, Teng,Wang, Ke-Hu,Huang, Danfeng,Xu, Changming,Su, Yingpeng,Hu, Yulai,Fu, Ying
p. 320 - 330
(2014/02/14)

One-step synthesis of 1-chloro-3-arylacetone derivatives from arylacetic acids
A practical one-step method has been developed to prepare α-chloroketones from readily available, inexpensive phenylacetic acid derivatives. The method utilizes the unique reactivity of an intermediate Mg.enolate dianion, which displays selectivity for the carbonyl carbon of chloromethyl carbonyl electrophiles. Decarboxylation of the intermediate occurs spontaneously during the reaction quench. The utility of the reaction products has been demonstrated through the total synthesis of the natural product cimiracemate B.
Zacuto, Michael J.,Dunn, Robert F.,Figus, Margaret
p. 8917 - 8925
(2015/01/09)

Highly efficient and environmentally benign preparation of Weinreb amides in the biphasic system 2-MeTHF/water
A straightforward chromatography-free preparation of Weinreb amides starting from acid halides has been achieved in the biphasic medium 2-MeTHF/water. Analytically pure compounds were isolated in excellent yields simply after removal of 2-MeTHF, which abs
Pace, Vittorio,Castoldi, Laura,Alcantara, Andres R.,Holzer, Wolfgang
p. 10158 - 10162
(2013/09/02)

Efficient carboazidation of alkenes using a radical desulfonylative azide transfer process
The radical-mediated carboazidation of terminal alkenes using electrophilic alkanesulfonyl azides is reported. A single reagent delivers the necessary electrophilic alkyl radical as well as the azido group, and good yields are obtained by using a moderate excess of the carboazidating reagent (1.5-2 equiv). Interestingly, in addition to the starting sulfonyl azide, this method requires only the use of a radical initiator, di-tert-butyldiazene. In terms of atom economy, this azide transfer reaction is close to ideal, as SO2 (1 equiv) is the only side product. The synthetic potential of this process has been demonstrated by a formal synthesis of the alkaloid lepadiformine C.
Weidner, Karin,Giroult, Andre,Panchaud, Philippe,Renaud, Philippe
supporting information; experimental part
p. 17511 - 17515
(2011/02/23)

Conformational preferences for some 2-substituted N-methoxy-N- methylacetamides through spectroscopic and theoretical studies
The analysis of the IR carbonyl band of the 2-substituted N-methoxy-N-methylacetamides Y-CH2C(O)N(OMe)Me (Y = F 1, OMe 2, OPh 3, Cl 4), supported by B3LYP/6-311++G(3df, 3pd) calculations along with the NBO analysis for 1-4, indicated the existence of cis-gauche conformers i.e. (c) and (g) for 1 and 3, (c1, c2) and (g1, g 2) for 2, and (c) and (g1, g2) for 4. In the gas phase, the g conformer population prevails over the c one, for 1 and 3, the (c1 + c2) population prevails over the (g1 + g2) one for 2, and the (g1 + g2) conformer population is more abundant than (c) one for 4. In n-hexane solution, the cis conformer is more abundant for 1-3. The occurrence of Fermi resonance in the νCO region, in n-hexane, precludes the estimative of relative populations of the (c, g1, g2) conformers for 4. The SCI-PCM calculations agree with the solvent effect on the νCO band component relative intensities for 1-3. NBO analysis showed that the n N → πco* orbital interaction is the main factor which stabilizes the gauche (g, g1, g2) conformers for 1-4 into a larger extent relative to the cis (c, c1, c2) ones. The nY → πco *, σC-Y → πco*, πco → σC-Y* and πco* → σC-Y* orbital interactions still contribute, but into a minor extent for the stabilization of the gauche conformers relative to the cis ones. The existence of some pyramidalization at the nitrogen atom of the Weinreb amides 1-4 is responsible for the occurrence of Yδ-(4)?Oδ-(9) and Y δ-(4)?Nδ-(7) short contacts in the gauche (g, g1, g2) conformers, which originates strong repulsive Coulombic interactions, acting in opposition to the large orbital stabilization of the gauche conformer with respect to the cis one. Therefore, a delicate balance of the Coulombic and orbital interactions seems to be responsible for the observed stabilization of the gauche (g, g1, g2) and cis (c, c1, c2) conformers, both in the gas phase and in the solution for 1-4. However, the cis conformer predominance, in non polar solvents, for the 2-substituted N-methoxy-N-methyl acetamides 1-3, bearing in α first raw (fluorine and oxygen) atoms, is in the opposite direction to the gauche conformer preference for the corresponding 2-substituted N,N-dialkyl-acetamides.
Olivato, Paulo R.,Da Silva Gomes, Roberto,Rodrigues, Alessandro,Reis, Adriana K.C.A.,Domingues, Nelson L.C.,Rittner, Roberto,Dal Colle, Maurizio
experimental part
p. 106 - 116
(2010/10/04)

Mechanistic insights into the rhodium-catalyzed intramolecular ketone hydroacylation
[Rh((fl)-DTBM-SEGPHOS)]BF4 catalyzes the intramolecular hydroacylation of ketones to afford seven-membered lactones in large enantiomeric excess. Herein, we present a combined experimental and theoretical study to elucidate the mechanism and origin of selectivity in this C-H bond activation process. Evidence is presented for a mechanistic pathway involving three key steps: (1) rhodium(I) oxidative addition into the aldehyde C-H bond, (2) insertion of the ketone C=O double bond into the rhodium hydride, and (3) C-O bond-forming reductive elimination. Kinetic isotope effects and Hammett plot studies support that ketone insertion isthe turnover-limiting step. Detailed kinetic experiments were performed using both 1,3- bis(diphenylphosphino)propane (dppp) and (R)-DTBM-SEGPH OS as ligands. With dppp, the keto-aldehyde substrate assists in dissociating a dimeric precatalyst 8 and binds an active monomeric catalyst 9. With [Rh((R)-DTBM-SEGPHOS)]BF4, there is no induction period and both substrate and product inhibition are observed. In addition, competitive decarbonylation produces a catalytically inactive rhodium carbonyl species that accumulates over the course of the reaction. Both mechanisms were modeled with a kinetics simulation program, and the models were consistent with the experimental data. Density functional theory calculations were performed to understand more elusive details of this transformation. These simulations support that the ketone insertion step has the highest energy transition state and reveal an unexpected interactionbetween the carbonyl-oxygen lone pair and a Rh d-orbital in this transi tion state structure. Finally, a model based on the calculated transition-state geometry is proposed to rationalize the absolute sense of enantioinduction observed using (R)-DTBM-SEGPHOS as the chiral ligand.
Shen, Zengming,Dornan, Peter K.,Khan, Hasan A.,Woo, Tom K.,Dong, Vy M.
supporting information; experimental part
p. 1077 - 1091
(2009/06/28)

MACROCYCLIC COMPOUNDS USEFUL AS INHIBITORS OF KINASES AND HSP90
Disclosed are macrocyclic compounds of formulae I-V,which are analogs of the pochonin resorcylic acid lactones, and processes for the preparation of the compounds. The compounds disclosed are useful as inhibitors of kinases and Heat Shock Protein 90 (HSP 90). Also disclosed are pharmaceutical compositions comprising an effective kinase-inhibiting amount or an effective HSP90-inhibiting amount of the compounds and methods for the treatment of disorders that are mediated by kinases and HSP90.
-
Page/Page column 148-149

(2010/11/30)

NOVEL SULFONAMIDE SUBSTITUTED CHROMAN DERIVATIVES USEFUL AS BETA-3 ADRENORECEPTOR AGONISTS
This invention relates to novel sulfonamide substituted chroman derivatives which are useful in the treatment of beta-3 receptor mediated conditions.
-
Page/Page column 57

(2008/12/07)

Rh-catalyzed carbonyl hydroacylation: an enantioselective approach to lactones
This communication describes the design and execution of a novel approach to forming chiral lactones via C-H bond activation. The strategy features an unprecedented enantioselective Rh-catalyzed hydroacylation of carbon-oxygen double bonds. Representative keto-aldehydes (derived from salicylaldehyde) undergo cyclization with complete regioselectivity to afford seven-membered lactones in great enantiomeric excess (≥99% ee). The basicity of the phosphine ligand is shown to play a critical role in promoting hydroacylation over competitive decarbonylation. Copyright
Shen, Zengming,Khan, Hasan A.,Dong, Vy M.
p. 2916 - 2917
(2008/10/09)

SYNTHESIS OF ALPHA-CHLORO OR ALPHA-FLUORO KETONES
A simple, high yielding synthesis of alpha -chloro ketones is described, involving acylation of Grignard and organolithium reagents with N-methoxy-M-methylchloroacetamide. The efficiency of the process is further enhanced by recycling N,O-dimethylhydroxylamine.
-
(2008/06/13)

SULFONAMIDE SUBSTITUTED CHROMAN DERIVATIVES USEFUL AS BETA 3 ADRENORECEPTOR AGONISTS
This invention related to novel sulfonamide substituted chroman derivatives which are useful in the treatment of beta-3 receptor mediated conditions.
-
(2011/11/14)

The sydnone ring as an ortho-director of lithiation. 2. Dilithiation of 3-phenylsydnone and regiospecific @?o-aryl acylation using N-methoxy-N-methylamides
Readily available 3-phenylsydnone (1) reacts with n-butyllithium/TMEDA to form the dilithio species 2 which can be regiospecifically acylated at the ortho-aryl position using N-methoxy-N-methylamides (Weinreb's amides).
Turnbull, Kenneth,Sun, Congcong,Krein, Douglas M.
p. 1509 - 1512
(2007/10/03)

Synthesis of α-chloro or fluoro ketones
A simple, high yielding synthesis of a-chloro ketones is described, involving acylation of Grignard and organolithium reagents with N-methoxy-N-methylchloroacetamide. The efficiency of the process is further enhanced by recycling N,O-dimethylhydroxylamine.
-
(2008/06/13)

Chemoselective Dieckmann-like condensations using N-methoxy-N-methylamides
The use of N-methoxy-N-methylamide as a chemoselective group in Dieckmann-like condensation is described. The chemoselectivity in these cyclizations is dependent on the counterion of the base employed.
Sibi, Mukund P.,Christensen, James W.,Kim, Sung-Gyu,Eggen, Marijean,Stessman, Chad,Oien, Larry
p. 6209 - 6212
(2007/10/02)

Total synthesis of the macrolide antibiotic cytovaricin
-
Evans,Kaldor,Jones,Clardy,Stout
p. 7001 - 7031
(2007/10/02)

A NEW SYNTHESIS OF α,β-UNSATURATED ALDEHYDES
The two carbon homologation of carbonyl compounds to α,β-unsaturated aldehydes is achieved by the Wittig-Horner reaction with N-methoxy N-methyl diethylphosphonoacetamide 1 followed by lithium aluminium hydride reduction.
Nuzillard, Jean-Marc,Boumendjel, Ahcene,Massiot, Georges
p. 3779 - 3780
(2007/10/02)