- Br?nsted acid catalysed chemo- andortho-selective aminomethylation of phenol
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We have developed a Br?nsted acid catalysed highlyortho-selective functionalization of free phenols with readily availableN,O-acetals under mild conditions, furnishing various corresponding aminomethylated phenol products in moderate to excellent yields. The salient features of this transformation include mild conditions, good substrate scope, excellentortho-selectivity, high efficiency, and ease of further transformation.
- Li, Dongdong,Liu, Lu,Peng, Dan,Tang, Zhiqiong,Yue, Yidi
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supporting information
p. 5777 - 5781
(2021/07/12)
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- Decarbonylative Synthesis of Aryl Nitriles from Aromatic Esters and Organocyanides by a Nickel Catalyst
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A decarbonylative cyanation of aromatic esters with aminoacetonitriles in the presence of a nickel catalyst was developed. The key to this reaction was the use of a thiophene-based diphosphine ligand, dcypt, permitting the synthesis of aryl nitrile without the generation of stoichiometric metal- or halogen-containing chemical wastes. A wide range of aromatic esters, including hetarenes and pharmaceutical molecules, can be converted into aryl nitriles.
- Iizumi, Keiichiro,Kurosawa, Miki B.,Isshiki, Ryota,Muto, Kei,Yamaguchi, Junichiro
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supporting information
p. 1555 - 1559
(2020/11/10)
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- Acetyl Acetone Covalent Triazine Framework: An Efficient Carbon Capture and Storage Material and a Highly Stable Heterogeneous Catalyst
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We present, for the first time, Covalent Triazine Frameworks functionalized with acetyl acetonate group (acac-CTFs). They are obtained from the polymerization of 4,4'-malonyldibenzonitrile under ionothermal conditions and exhibit BET surface areas up to 1626 m2/g. The materials show excellent CO2 uptake (3.30 mmol/g at 273 K and 1 bar), H2 storage capacity (1.53 wt% at 77 K and 1 bar) and a good CO2/N2 selectivity (up to 46 at 298 K). The enhanced CO2 uptake value and good selectivity are due to the presence of dual polar sites (N and O) throughout the material. In addition, acac-CTF was used to anchor VO(acac)2 as a heterogeneous catalyst. The V@acacCTF showed outstanding reactivity and reusability for the modified Mannich-type reaction with a higher turnover number than the homogeneous catalyst. The higher reactivity and reusability of the catalyst comes from the coordination of the vanadyl ions to the acetyl acetonate groups present in the material. The strong metalation is confirmed from Fourier Transform Infrared analysis, 13C MAS NMR spectral analysis and X-ray photoelectron spectroscopy measurement. Detailed characterization of the V@acac-CTF reveals that electron donation from O^O of the acetyl acetonate group to VO(acac)2, combined with the very high surface area of acac-CTF, is responsible for the stabilization of the catalyst. Overall, this contribution highlights the necessity of stable catalytic binding sites on heterogeneous supports to fabricate greener catalysts for sustainable chemistry.
- Jena, Himanshu Sekhar,Krishnaraj, Chidharth,Wang, Guangbo,Leus, Karen,Schmidt, Johannes,Chaoui, Nicolas,Van Der Voort, Pascal
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- The modified-Mannich reaction: Conversion of arylboronic acids and subsequent coupling with paraformaldehyde and amines toward the one-pot synthesis of Mannich bases and benzoxazines
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A modified Mannich reaction has been developed for the synthesis of Mannich bases and benzoxazines via the oxidative hydroxylation of arylboronic acids and subsequent coupling with paraformaldehyde and amines in one pot. This modified Mannich reaction is easily carried out to afford the target products in good to excellent yields and tolerates a variety of functional groups.
- Liu, Juan,Yuan, Gaoqing
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supporting information
p. 1470 - 1473
(2017/03/23)
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- Cu(II)-Catalyzed ortho-Selective Aminomethylation of Phenols
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A Cu(II)-catalyzed ortho-selective functionalization of free phenols with trifluoroborates to afford Csp2-Csp3 coupling products under mild conditions has been developed. A variety of functional groups on the phenol and the potassium aminomethyltrifluoroborate substrates were found compatible, furnishing the corresponding products in moderate to excellent yields. A single-electron transfer radical coupling mechanism involving a six-membered transition state is proposed to rationalize the high levels of ortho-selectivity in the reaction. This protocol provides straightforward access to ortho-aminomethyl-substituted phenols, unnatural amino acids and other bioactive small molecules.
- Dai, Jin-Ling,Shao, Nan-Qi,Zhang, Jin,Jia, Run-Ping,Wang, Dong-Hui
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supporting information
p. 12390 - 12393
(2017/09/23)
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- Redox-neutral α-oxygenation of amines: Reaction development and elucidation of the mechanism
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Cyclic secondary amines and 2-hydroxybenzaldehydes or related ketones react to furnish benzo[e][1,3]oxazine structures in generally good yields. This overall redox-neutral amine α-C-H functionalization features a combined reductive N-alkylation/oxidative α-functionalization and is catalyzed by acetic acid. In contrast to previous reports, no external oxidants or metal catalysts are required. Reactions performed under modified conditions lead to an apparent reductive amination and the formation of o-hydroxybenzylamines in a process that involves the oxidation of a second equivalent of amine. A detailed computational study employing density functional theory compares different mechanistic pathways and is used to explain the observed experimental findings. Furthermore, these results also reveal the origin of the catalytic efficiency of acetic acid in these transformations.
- Richers, Matthew T.,Breugst, Martin,Platonova, Alena Yu.,Ullrich, Anja,Dieckmann, Arne,Houk,Seidel, Daniel
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p. 6123 - 6135
(2014/05/20)
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- Anionic ortho-fries rearrangement, a facile route to arenol-based mannich bases
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Phenol and 1-naphthol-based carbamates undergo the anionic ortho-Fries rearrangement to their corresponding amides. Bulky substitution at position 8 of 1-naphthol-based carbamates makes the rearrangement an exclusive reaction, even at -90 C, under a variety of conditions. The amides can be efficiently reduced to the corresponding Mannich bases. A novel route to 7-[(dialkylamino)methyl]-8- hydroxy-1-naphthaldehydes is presented.
- Assimomytis, Nikos,Sariyannis, Yiannis,Stavropoulos, Georgios,Tsoungas, Petros G.,Varvounis, George,Cordopatis, Paul
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experimental part
p. 2777 - 2782
(2010/03/03)
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- Regioselective mannich reaction of phenols under high pressure using dichloromethane as C1 unit
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Regioselectivity in Mannich reaction of 4-, 3-, and 2-substituted phenols with typical heterocyclic amines are investigated under reaction conditions developed by us. Phenol and 4-alkyl, and 4-chlorophenols in the title reaction predominantly gave the corresponding 2-(aminomethyl)phenols, while 4-methoxyphenol afforded, in addition to the mono(aminomethyl)phenols, a considerable amount of the bis adducts. Peculiarly enough, 3-methylphenol with amines afforded 3-methyl-4-(aminomethyl)phenols whereas 2-methylphenol produced 2-methyl-6-(aminomethyl)phenols.
- Matsumoto, Kiyoshi,Joho, Kouta,Mimori, Seisuke,Iida, Hirokazu,Hamana, Hiroshi,Kakehi, Akikazu
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scheme or table
p. 1061 - 1067
(2009/06/28)
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- Substituents on quinone methides strongly modulate formation and stability of their nucleophilic adducts
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Electronic perturbation of quinone methides (QM) greatly influences their stability and in turn alters the kinetics and product profile of QM reaction with deoxynucleosides. Consistent with the electron-deficient nature of this reactive intermediate, electron-donating substituents are stabilizing and electron-withdrawing substituents are destabilizing. For example, a dC N3-QM adduct is made stable over the course of observation (7 days) by the presence of an electron-withdrawing ester group that inhibits QM regeneration. Conversely, a related adduct with an electron-donating methyl group is very labile and regenerates its QM with a half-life of approximately 5 h. The generality of these effects is demonstrated with a series of alternative quinone methide precursors (QMP) containing a variety of substituents attached at different positions with respect to the exocyclic methylene. The rates of nucleophilic addition to substituted QMs measured by laser flash photolysis similarly span 5 orders of magnitude with electron-rich species reacting most slowly and electron-deficient species reacting most quickly. The reversibility of QM reaction can now be predictably adjusted for any desired application.
- Weinert, Emily E.,Dondi, Ruggero,Colloredo-Melz, Stefano,Frankenfield, Kristen N.,Mitchell, Charles H.,Freccero, Mauro,Rokita, Steven E.
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p. 11940 - 11947
(2007/10/03)
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- ISOQUINOLINE-5-SULFONIC ACID AMIDES AS INHIBITORS OF AKT (PROTEIN KINASE B)
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The present invention relates to compounds Formula (I): as inhibitors of AKT activity, which are useful for the treatment of susceptible neoplasms and viral infections.
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- A modified Mannich-Type reaction catalyzed by VO(acac)2
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(Equation Presented) A fackile VO(acac)2-catalyzed in situ generation of iminium ions from amine N-oxides and their participation in a modified Mannich-type reaction is described.
- Hwang, Der-Ren,Uang, Biing-Jiun
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p. 463 - 466
(2007/10/03)
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- Alkylation of amino acids and glutathione in water by o-Quinone methide. Reactivity and selectivity
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o-Quinone methide (1) has been produced in water both thermally and photochemically from (2-hydroxybenzyl)trimethylammonium iodide (2). Michael addition reactions of 1 to various amines, and sulfides, including amino acids and glutathione have been carried out, obtaining alkylated adducts (3-16) in fairly good to quantitative yields. The reaction rate and selectivity of 1 toward nitrogen and sulfur nucleophiles, in competition with the hydration reaction, have been investigated at different pH by laser flash photolysis technique. The observed reactivity spans 7 orders of magnitude on passing from water (kNu = 5.8 M-1 s-1) to the most reactive nucleophile (2.8 × 108 M-1 s-1, 2-mercaptoethanol under alkaline conditions). These are the first direct reaction rate measurements of nucleophilic addition to the parent o-quinone methide (1). Competition experiments provided strong kinetic support to the involvement of free 1 as an intermediate in both thermal and photochemical reactions. Furthermore, several alkylation adducts regenerate 1 either by heating (9, 10, 13, and 14) or by irradiation (9, 11-13, 16). Such a thermal and photochemical reversibility of the alkylation process opens a new perspective for the use and application of such adducts as o-QM molecular carriers.
- Modica,Zanaletti,Freccero,Mella
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- A reductive amination of carbonyls with amines using decaborane in methanol
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Aldehydes and ketones were easily converted to the corresponding amines by the reaction of amines in methanol using decaborane (B10H14) at room temperature under nitrogen. The reaction is simple and efficient. The Royal Society of Chemistry 2000.
- Bae, Jong Woo,Lee, Seung Hwan,Cho, Young Jin,Yoon, Cheol Min
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p. 145 - 146
(2007/10/03)
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- Synthesis of phenols and naphthol with n-morpholinomethyl pendants and their dimethylgallium complexes: Crystal structure of dimethylgallium-[4-nitro-2-(n-morpholinomethyl)-1-phenoxide]
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The one-pot Mannich reaction was used to synthesize 2-(n-morpholinomethyl)-1-phenol (1a), 4-methyl-2-(n-morpholinomethyl)-1-phenol (1b), 4-chloro-2-(n-morpholinomethyl)-1-phenol (1c), 4-nitro-2-(n-morpholinomethyl)-1-phenol (1d), and 1-(n-morpholinomethyl)-naphthol (1e). The dimethylgallium complexes of these compounds have been prepared, and compound 2d has been determined by X-ray crystallography. The complex 2d crystallized with one unit having two identical molecules which have intermolecular contacts between the two phenyls caused by face to face π-π stacking. The Ga-O bond distances are noticeably shorter than in the other dimethylgallium phenoxides reported.
- Tian, Jing-Zhi,Zhang, Jin-Qi,Shen, Xi,Zou, Hui-Xian
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p. 240 - 245
(2007/10/03)
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- PREPARATION AND PROPERTIES OF 2-(DIALKYLAMINOMETHYL)CYCLOHEXYL AND 2-(DIALKYLAMINOMETHYL)PHENYL CARBANILATES
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A series of 2-(dialkylaminomethyl)cyclohexyl and 2-(dialkylaminomethyl)phenyl esters of substituted carbanilic acid have been prepared and their identity verified by elemental analysis and evaluation of IR and 13C NMR spectra.The spectral results have bee
- Bradlerova, Alena,Pronayova, Nadezda,Misikova, Eva,Durinda, Jan
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p. 1854 - 1865
(2007/10/02)
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- CONVENIENT SYNTHESIS OF 2-THIONAPHTHYLMETHYL ISOCYANIDE: A USEFUL REAGENT FOR METHYL ISOCYANIDE TRANSFER
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The crystalline 2-thionaphthylmethyl isocyanide (1), prepared from the novel N-(formamidomethyl)-N-benzyl morpholinium iodide (2), via transfer of elements of CH2NHCHO, is totally devoid of pervasive odour.The cyclo-addition of the conjugate base of (1) to nitriles followed by desulfurization, under very mild conditions, provides an attractive route to imidazoles.
- Ranganathan, S.,Singh, W. P.
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p. 1435 - 1436
(2007/10/02)
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