- Synthesis of 5-Vinyl-2-isoxazolines by Palladium-Catalyzed Intramolecular O-Allylation of Ketoximes
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An efficient method for the synthesis of 5-vinyl-2-isoxazolines by Pd-catalyzed intramolecular O-allylation of ketoximes has been developed. The reaction involves Pd(0)-catalyzed π-allyl formation via leaving group ionization or Pd(II)-catalyzed allylic C-H activation followed by intramolecular nucleophilic oxime oxygen attack. This methodology has been elaborated to various value-added products by epoxidation, Wacker oxidation, cross-metathesis, hydroboration-oxidation, dihydroxylation, and catalytic hydrogenation.
- Fernandes, Rodney A.,Gangani, Ashvin J.,Panja, Arpita
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supporting information
p. 6227 - 6231
(2021/08/18)
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- Arylboronic Acid-Catalyzed C-Allylation of Unprotected Oximes: Total Synthesis of N-Me-Euphococcine
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O-Unprotected keto-and aldoximes are readily C-allylated with allyl diisopropyl boronate in the presence of arylboronic acid catalysts to yield highly substituted N-α-secondary and tertiary homoallylic hydroxylamines. The method was used in the total synthesis of the trace alkaloid N-Me-Euphococcine.
- Kürti, László,Kattamuri, Padmanabha V.,Siitonen, Juha H.,Yousufuddin, Muhammed
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supporting information
(2020/03/24)
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- CuCl2-catalyzed N[sbnd]O bond cleavage of oxime esters: Approach to imidazoheterocycles and furo[3,2-c]chromenyl fused imidazoles
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An articulate approach to a diverse set of imidazoheterocycles in good to high yields via a copper-catalyzed aza-annulation of several oxime esters with a group of 2-amino-azaarenes was developed. The above cyclization reaction probably proceeds via a single electron transfer process which embodies a new technique for creating two new C[sbnd]N bonds for imidazole ring synthesis. Gratifyingly, the implementation of this chemistry could be further stretched to the synthesis of a novel class of fused imidazoles bearing a furo[3,2-c]chromene moiety via a sequential C[sbnd]N bond formation, followed by C(sp2)-H functionalization/5-endo-dig-oxacyclization (C[sbnd]C and C[sbnd]O bonds) of in situ produced fused imidazoles with cyclic enynones in the presence of copper(II) as a π-electrophilic Lewis acid catalyst.
- Gudimella, Santosh K.,Kaur, Amanpreet,Kumar, Ram,Samanta, Sampak
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supporting information
(2020/07/08)
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- Copper(0)/PPh3-Mediated Bisheteroannulations of o-Nitroalkynes with Methylketoximes Accessing Pyrazo-Fused Pseudoindoxyls
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A copper(0)/PPh3-mediated cascade bisheteroannulation reaction of o-nitroalkynes with methylketoximes has been developed that provides viable access to a diverse range of pyrazo-fused pseudoindoxyl compounds. Synthetically useful functional groups including sensitive C-I bonds are compatible with this system. Mechanistic studies suggest a reaction cascade involving sequential PPh3-mediated deoxygenative cycloisomerization and copper-catalyzed [3 + 2] pyrazo-annulation.
- Meng, Huanxin,Xu, Zhenhua,Qu, Zhonghua,Huang, Huawen,Deng, Guo-Jun
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supporting information
p. 6117 - 6121
(2020/08/12)
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- SO2F2-Activated Efficient Beckmann Rearrangement of Ketoximes for Accessing Amides and Lactams
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A novel, mild and practical protocol for the efficient activation of the Beckmann rearrangement utilizing the readily available and economical sulfuryl fluoride (SO2F2 gas) has been developed. The substrate scope of the operationally simple methodology has been demonstrated by 37 examples with good to nearly quantitative isolated yields (over 90 % yield in most cases) in a short time, including B(OH)2, COOH, NH2, and OH substituted substrates. A tentative mechanism was proposed involving formation and elimination of key intermediate, sulfonyl ester.
- Zhang, Guofu,Zhao, Yiyong,Xuan, Lidi,Ding, Chengrong
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supporting information
p. 4911 - 4915
(2019/07/31)
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- A preparation method of the compound including wo and using the organic phosphoric acid ester compound detection method
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The invention discloses a method for preparing the compounds including wo using the organic phosphoric acid ester compound of the detection method. Including wo compound preparation method is as follows: the reaction substrate is soluble in the reaction solution, then adding hydroxylamine hydrochloride, the mixture is heated reaction; cooling to room temperature, collecting the reaction product on a short silica gel column and purification, eluting with organic solvent, the final product is obtained. The use of the above-mentioned compound detection organic phosphoric acid ester compound include: (1) including wo compound as a probe in a solution to be detected is added in the organophosphorus ester compound, reaction fluorescence detection; (2) in a two-dimensional metal carbide or nitride including wo compound is added, then the load on the glass carbon electrode, soaked in the but in the detection solution, after reaction of the electrochemical detection. The method has fast detection speed, high sensitivity, selectivity, stability is good, the false positive low and the like, it has broad application prospects.
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Paragraph 0032; 0033
(2019/05/22)
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- Access to 2-Aroylthienothiazoles via C-H/N-O Bond Functionalization of Oximes
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A novel strategy for the synthesis of 2-aroylthienothiazoles via C-H/N-O bond functionalization of ketoximes is developed. This reaction features excellent step- and atom-economy, as well as broad substrate scope. Various common ketoximes, even vinyl ketoximes, were efficiently converted to 2-aroylthienothiazoles. Preliminary mechanistic studies indicated that the radical process should be involved in this transformation. Moreover, the product exhibited good coordination with Cu(II), showing the potential application in the metal coordination field.
- Zhou, Peiqi,Huang, Yubing,Wu, Wanqing,Zhou, Jiaming,Yu, Wentao,Jiang, Huanfeng
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supporting information
p. 9976 - 9980
(2019/12/24)
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- Enantioselective Hydrosilylation of Imines Catalyzed by Chiral Zinc Acetate Complexes
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A series of zinc acetate complexes with optically pure diphenylethanediamine (DPEDA)-derived ligands have been employed as enantioselective catalyst for the hydrosilylation of various imines. High control of stereoselectivity (up to 97% ee) and excellent yields (up to 96%) were gained for a broad range of N-phosphinoylimines by using (R,R)-N,N′-dibenzyl-1,2-diphenylethane-1,2-diamine. This is the first successful application of an air-stable and environmentally friendly chiral Zn(OAc)2 complex instead of the previously used harmful diethylzinc in the asymmetric reduction of the C=N double bond.
- Bez?ada, Agata,Szewczyk, Marcin,Mlynarski, Jacek
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p. 336 - 342
(2016/01/15)
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- Cobalt(III)-Catalyzed Dehydrative [4+2] Annulation of Oxime with Alkyne by C-H and N-OH Activation
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Efficient, scalable cobalt-catalyzed redox-neutral [4+2] annulation of readily available oximes and alkyne is reported. The developed synthetic methodology is widely applicable and tolerates various functional groups including heterocycles. A stable CpCoIII neutral complex is employed as the catalyst for this redox-neutral [4+2] annulation reaction, which progresses smoothly by way of a reversible cyclometallation without any external oxidizing agent, and produces only water as the side product.
- Sen, Malay,Kalsi, Deepti,Sundararaju, Basker
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supporting information
p. 15529 - 15533
(2015/11/03)
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- TETRAZOLINONE COMPOUND AND USE THEREOF
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The compound represented by formula (1): wherein R4 and R5 each represents a hydrogen atom, a halogen atom, or a C1-C3 alkyl group; R6 represents a C1-C4 alkyl group, a C3-C6 cycloalkyl group, or the like; R7, R8, and R9 each represents a hydrogen atom, a halogen atom, or the like; R10 represents a C1-C3 alkyl group, or the like; R13 represents a C1-C3 alkyl group, or the like; and Q represents a phenyl group, or the like; has an excellent control effect on pests.
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Paragraph 0844-0845
(2015/11/16)
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- Asymmetric synthesis of nonracemic primary amines via spiroborate-catalyzed reduction of pure (E)- and (Z)-O-benzyloximes: Applications toward the synthesis of calcimimetic agents
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Highly enantiopure (1-aryl)- and (1-naphthyl)-1-ethylamines were synthesized by the borane-mediated reduction of single-isomeric (E)- and (Z)-O-benzyloxime ethers using the stable spiroborate ester derived from (S)-diphenyl valinol and ethylene glycol as the chiral catalyst. Primary (R)-arylethylamines were prepared by the reduction of pure (Z)-ethanone oxime ethers in up to 99% ee using 15% of catalyst. Two convenient and facile approaches to the synthesis of new and known calcimimetic analogues employing enantiopure (1-naphthalen-1-yl)ethylamine as chiral precursor are described.
- Ou, Wenhua,Espinosa, Sandraliz,Meléndez, Héctor J.,Farré, Silvia M.,Alvarez, Jaime L.,Torres, Valerie,Martínez, Ileanne,Santiago, Kiara M.,Ortiz-Marciales, Margarita
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p. 5314 - 5327
(2013/07/25)
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- Asymmetric transfer hydrogenation of ketimines using well-defined iron(II)-based precatalysts containing a PNNP ligand
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Well-defined iron(II)-based complexes containing PNNP ligands catalyze a highly enantioselective reduction of N-(diphenylphosphinoyl)- and N-(p-tolylsulphonyl)-ketimines. Under mild conditions and low catalyst loading, the ketimines are successfully reduced to the corresponding amines in enantiomeric excess ranging from 94 to 99%.
- Mikhailine, Alexandre A.,Maishan, Mazharul I.,Morris, Robert H.
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supporting information
p. 4638 - 4641
(2012/10/29)
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- Europium(III) triflate-catalyzed Trofimov synthesis of polyfunctionalized pyrroles
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The synthesis of polyfunctionalized pyrroles by reaction of a ketoxime with dimethyl acetylenedicarboxylate using europium(III) triflate as the catalyst is described. Copyright
- Madabhushi, Sridhar,Vangipuram, Venkata Sairam,Mallu, Kishore Kumar Reddy,Chinthala, Narsaiah,Beeram, China Ramanaiah
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supporting information; body text
p. 1413 - 1416
(2012/07/13)
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- Efficient synthesis and practical resolution of 1-(naphthalen-1-yl) ethanamine, a key intermediate for cinacalcet
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An efficient synthesis of 1-(naphthalen-1-yl)ethanamine (RS-2) and its practical resolution to optically pure (1R)-(naphthalen-1-yl)ethanamine (R-(+)-2), a key intermediate in the synthesis of cinacalcet hydrochloride (1), is described. The resolution of RS-2 using R-(-)-mandelic acid as a resolving agent in ethanol was established on an industrial scale to give pure R-(+)-2 with >99.8% ee after liberation of the amine from its mandelate salt. An efficient process for the racemization of undesired isomer S-(-)-2 is also provided to maximize the yield of desired enantiomer.
- Mathad, Vijayavitthal T.,Shinde, Gorakshanath B.,Ippar, Sharad S.,Niphade, Navnath C.,Panchangam, Raghavendra K.,Vankawala, Pravinchandra J.
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experimental part
p. 341 - 346
(2011/04/15)
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- Synthesis and biological evaluation of some new naphthyl derivatives as anti-microbial activity
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IN CONECTION with our previous interest in developing new approaches for synthesis of heterocyclic utilizing readily obtainable starting materials, we reported here synthesis of a new heterocyclic utilizing 1-acetyl naphthalene. Reaction of acetyl naphtha
- El-Metwally, Amira M.
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p. 129 - 139
(2013/05/21)
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- Synthesis of isoquinolines via rhodium(III)-catalyzed dehydrative C-C and C-N coupling between oximines and alkynes
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Isoquinolines have been synthesized from the redox-neutral dehydrative C-N and C-C cross-coupling between oximines and alkynes using a catalytic amount of (pentamethylcyclopentadiene)rhodium dichloride dimer {[RhCp*Cl 2]2} and cesium
- Zhang, Xingping,Chen, Dan,Zhao, Miao,Zhao, Jing,Jia, Aiqun,Li, Xingwei
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supporting information; experimental part
p. 719 - 723
(2011/05/08)
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- Ruthenium-catalyzed hydrovinylation of N-acetylenamines leading to amines with a quaternary carbon center
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A catalytic hydrovinylation of N-acetylenamines with ethylene is reported. This new hydrovinylation reaction is catalyzed by a ruthenium hydride complex, RuHCl(CO)(PCy3)2, providing a series of N-acetylamines with a quaternary carbon center with up to 99% yield.
- Wang, Qiu-Shi,Xie, Jian-Hua,Li, Wei,Zhu, Shou-Fei,Wang, Li-Xin,Zhou, Qi-Lin
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supporting information; scheme or table
p. 3388 - 3391
(2011/08/21)
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- On the origins of diastereoselectivity in the alkylation of enolates derived from N-1-(1′-Naphthyl)ethyl-O-tert-butylhydroxamates: Chiral Weinreb amide equivalents
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(Chemical Equation Presented) The stereochemical outcome observed upon alkylation of enolates derived from N-1-(1′-naphthyl)ethyl-O-tert- butylhydroxamates (chiral Weinreb amide equivalents) may be rationalized by a chiral relay mechanism. Deprotonation withKHMDS leads to a nonchelated (Z)-enolate inwhich the oxygen atoms adopt an anti-periplanar conformation. The configuration of the N-1-(1′-naphthyl)ethyl group dictates the conformation of the O-tert-butyl group and the configuration adopted by the adjacent pyramidal nitrogen atom. Highly diastereoselective enolate alkylation then proceeds anti to both the bulky tert-butyl group (sterically driven) and the N-lone pair (stereoelectronically driven).
- Davies, Stephen G.,Goodwin, Christopher J.,Hepworth, David,Roberts, Paul M.,Thomson, James E.
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supporting information; experimental part
p. 1214 - 1227
(2010/04/26)
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- The Remarkable Effect of E/Z Isomers on the Catalytic Asymmetric Hydrogenation of Oximes
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The E and Z isomers of 1-acetonaphthone oxime are isolated, characterized, and subjected to catalytic asymmetric hydrogenation; the chiral products from the asymmetric hydrogenation reflect the effect of the E and Z isomers on the enantioselectivity of the reaction.
- Chan, Albert S. C.,Chen, Chih-Chiang,Lin, Ching-Wen,Lin, Ying-Chih,Cheng, Ming-Chu,Peng, Shie-Ming
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p. 1767 - 1768
(2007/10/02)
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- Direct carbohydroximoylation of aromatics with primary nitroalkanes in triflic acid (TFSA)
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Primary nitroalkanes react with aromatics in triflic acid to yield arylated oximes at 70-80°C.
- Coustard, Jean-Marie,Jacquesy, Jean-Claude,Violeau, Bruno
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p. 8085 - 8086
(2007/10/02)
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- Diastereoselectivity of Organometallic Additions to Nitrones Bearing Sterogenic N-Substituents
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The diastereoselectivity of organometallic additions to nitrones bearing stereogenic α-arylethyl, β-methoxyalkyl, and β-(silyloxy)alkyl substituents on nitrogen has been investigated.High and complementary diastereoselectivity (90-94percent) was observed in the additions of Grignard reagents to nitrones (e.g. 22 and 23) bearing the potentially chelating β-methoxyalkyl group.However, the opposite selectivity resulted from the reaction of methylmagnesium bromide with the corresponding silyl ether (27).The relative stereochemistry of selected hydroxylamine adducts wasestablished by reduction of their phosphate and carbonate derivatives to known amines (37a,b and 39), by periodate cleavage of a β-hydroxy hydroxylamine (41b), and by various correlations (Scheme II).The high facial diastereoselectivity observed with the N-(β-methoxyalkyl)nitrones is explained by a simple chelation model (Scheme III).
- Chang, Zen-Yu,Coates, Robert M.
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p. 3464 - 3474
(2007/10/02)
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