- Triethylsiloxymethyl-N,N-dimethylamine, Et3SiOCH2NMe2: A Dimethylaminomethylation (Mannich) Reagent for O–H, S–H, P–H and Aromatic C–H Systems
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Triethylsiloxymethylamine, Et3SiOCH2NMe2, readily synthesized in high yield by the hydrosilylation reaction between Et3SiH and DMF, is an excellent (N,N-dimethylamino)methyl transfer agent to a representative range of aliphatic alcohols, thiols, and Ph2PH (E–H) materials. The reactions are almost instantaneous at room temperature in inert solvents and require no activating agents to produce E–CH2NMe2 products in high yields and illustrate the title compound as an excellent addition to the family of organic reagents. For aromatic alcohols, electrophilic substitution of the aromatic ring occurs in high yield. Crystal structures of new materials such as the cholestero–CH2NMe2 derivative, 2–4-[bis(N,N-dimethylamino)methyl]-1-naphthol, and the phosphine oxide derived from Ph2PCH2NMe2 are reported.
- Gonzalez, Paulina E.,Sharma, Hemant K.,Chakrabarty, Sanchita,Metta-Maga?a, Alejandro,Pannell, Keith H.
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- Mannich bases of phenolic azobenzenes possessing cytotoxic activity
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A number of arylazophenols 1 were converted into the corresponding mono Mannich bases 2 from which two quaternary salts 3a,b and an ester 3c were prepared. A series of bis Mannich bases 4 were also synthesized. The angles (φ) made between one of the aryl rings and the adjacent azo linkage were determined by electronic absorption spectroscopy. X-ray crystallographic data were obtained for some of the Mannich bases. The compounds were evaluated against murine P388 D1 and L1210 cells and two human T-lymphocyte (Molt 4, CEM) lines, and most of the derivatives were also screened against a panel of human tumour cell lines. A number of correlations were noted between cytotoxicity and various physicochemical constants as well as some structural features determined by X-ray crystallography. Several of the Mannich bases were shown to have mutagenic properties using the λ RK mutatest; the compounds in series 2 and 4 have the ability to penetrate the central nervous system, as revealed by their anticonvulsant properties. While series 2-4 have the potential to deaminate forming ortho quinone methides which would be capable of alkylating cellular thiols, the results of stability studies suggest that the bioactivities noted were due to the molecules per se.
- Dimmock,Erciyas,Kumar,Hetherington,Quail,Pugazhenthi,Arpin,Hayes,Allen,Halleran,De Clercq,Balzarini,Stables
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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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- Diazaborines oxidize slowly with H2O2 but rapidly with peroxynitrite in aqueous buffer
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Reactive oxygen species (ROS) such as hydrogen peroxide (H2O2) and peroxynitrite (ONOO?) oxidize arylboronic acids to their corresponding phenols. When used in molecular imaging probes and in ROS-responsive molecules, however, simple arylboronic acids struggle to discriminate between H2O2 and ONOO? because of their fast rate of reaction with both ROS. Here, we show that diazaborines (DABs) react slowly with H2O2 but rapidly with peroxynitrite in an aqueous buffer. In addition to their slow reaction with H2O2, the immediate product of DAB oxidation with H2O2 and ONOO? can yield a kinetically trapped CN Z-isomer that slowly equilibrates with its E-isomer. Taken together, our work shows that diazaborines exhibit enhanced kinetic discrimination between H2O2 and ONOO? compared to arylboronic acids, opening up new opportunities for diazaborine-based tools in chemical biology.
- Domaille, Dylan W.,Golzwarden, Julian V. A.,Haggett, Jack G.,Han, Gun Su,Moser, Angela R.,Vyas, Shubham
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supporting information
p. 995 - 999
(2022/02/16)
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- Photo-Induced ortho-C-H Borylation of Arenes through in Situ Generation of Rhodium(II) Ate Complexes
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Photoinduced in situ "oxidation"of half-sandwich metal complexes to "high-valent"cationic metal complexes has been used to accelerate catalytic reactions. Here, we report the unprecedented photoinduced in situ "reduction"of half-sandwich metal [Rh(III)] complexes to "low-valent"anionic metal [Rh(II)] ate complexes, which facilitate ligand exchange with electron-deficient elements (diboron). This strategy was realized by using a functionalized cyclopentadienyl (CpA3) Rh(III) catalyst we developed, which enabled the basic group-directed room temperature ortho-C-H borylation of arenes.
- Araujo Dias, Ant?nio Junio,Nagashima, Yuki,Tanaka, Jin,Tanaka, Ken
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p. 11325 - 11331
(2021/08/03)
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- The role of β-cyclodextrin in mediating regioselective dimethylaminomethylation of phenol
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Regioselective reactions with supramolecular control are of great interest. Herein, the para-regioselectivity in the Mannich reaction of phenol with formaldehyde and dimethylamine was achieved with the use of β-cyclodextrin (β-CD), giving 4-(N,N-dimethylaminomethyl)phenol (p-AP) as major product. 1H NMR and ITC measurements of the binding of β-CD with the reactants and the products o- and p-AP revealed a new mechanism, in which β-CD includes p-AP instead of phenol to control the reaction regioselectivity. This product-inclusion mechanism is remarkably different to the known reactant-inclusion process.
- Wu, Wen-Hai,Duan, Jiang,Wei, Ting,Tu, Hai-Yang,Zhang, Ai-Dong
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supporting information
p. 360 - 365
(2017/12/26)
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- Anti-tumor application of tocopheroxyl nitrogen oxide as HDAC (Histone Deacetylase) inhibitor
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The invention discloses anti-tumor application of tocopheroxyl nitrogen oxide as an HDAC (Histone Deacetylase) inhibitor. A compound has a structural general formula as shown in a formula (I), and the compound has a potential inhibition effect on HDAC, so that more nitrogen and oxygen can be further provided for a ZBG (Zinc Binding Group), multi-length survey and the like can be carried out on a linker, structure modification can be carried out on the existing basis, and the functions of an inhibitor having good selectivity on HDAC subtype and other target points are expected to be found. According to the anti-tumor application disclosed by the invention, synthetic raw materials are relatively cheap, the technology is simple, the purity is higher, the cost is lower, and used reagents are all relatively safe. The compound is expected to be used as a novel HDAC inhibitor type anti-tumor medicine which is strong in selectivity, high in efficiency and low in toxicity.
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Paragraph 0064-0066
(2017/09/18)
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- Convenient synthesis of 2-Amino-4H-chromenes from photochemically generated o-quinone methides and malononitrile
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2-Amino-4H-chromenes were synthesized in moderate to good yields by the reaction of o-quinone methides photochemically generated from o-(dimethylaminomethyl)phenols with malononitrile. This method was applicable to the synthesis of fluorinated chromenes that were difficult to obtain by other methods. In addition, o-(hydroxymethyl)phenols could be used for the reaction in the presence of tertiary amine bases.
- Fujiwara, Makoto,Sakamoto, Masanori,Komeyama, Kimihiro,Yoshida, Hiroto,Takaki, Ken
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- Oxidative ortho-amino-methylation of phenols via C-H and C-C bond cleavage
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Initiated by CCl3Br, phenols undergo efficient ortho-selective oxidative cross dehydrogenative coupling (CDC) with trimethylamine. When tetramethylethylenediamine (TMEDA) is used instead of trimethylamine, oxidative carbon-carbon activation coupling (CAC) could occur to give the same salicylamines together with CDC by-products. These reactions are accelerated by a gold salt.
- Sun, Wenbo,Lin, Huacan,Zhou, Wenyu,Li, Zigang
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p. 7491 - 7494
(2014/02/14)
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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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- Ruthenium-catalyzed /V-alkylation of amines and sulfonamides using borrowing hydrogen methodology
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The alkylation of amines by alcohols has been achieved using 0.5 mol percent [Ru(p-cymene)CI2]2 with the bidentate phosphines dppf or DPEphos as the catalyst. Primary amines have been converted into secondary amines, and secondary amines into tertiary amines, including the syntheses of Piribedil, Tripelennamine, and Chlorpheniramine. A/-Heterocyclization reactions of primary amines are reported, as well as alkylation reactions of primary sulfonamides. Secondary alcohols requiremore forcing conditions than primary alcohols but are still effective a lkylating agents in the presence of this catalyst.
- Hamid, M. Haniti S. A.,Allen, C. Liana,Lamb, Gareth W.,Maxwell, Aoife C.,Maytum, Hannah C.,et al.
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supporting information; experimental part
p. 1766 - 1774
(2009/07/25)
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- Synthesis of the β2 Agonist (R)-Salmeterol Using a Sequence of Supported Reagents and Scavenging Agents
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(Matrix Presented) The enantioselective synthesis of (R)-salmeterol has been achieved by using a sequence of supported reagents and sequestering agents. The saligenin core was installed by a regiospecific alkylation and a chiral auxiliary approach was employed to introduce the desired stereochemistry via a diastereoselective reduction.
- Bream, Robert N.,Ley, Steven V.,Procopiou, Panayiotis A.
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p. 3793 - 3796
(2007/10/03)
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- The activation of aminals and aminol ethers by sulfur dioxide and their reactions with electron rich aromatic compounds
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Reactions of bis(dialkylamino)methanes and ethoxydialkylaminomethanes with nucleophilic aromatic heterocycles in the presence of sulfur dioxide result in the formation of the expected Mannich bases in good yields. Reactions of phenols are similarly activated by sulfur dioxide which lead to improved regioselectivity: in particular the reactions of 2,5-dimethylphenol result in the formation of 2-dialkylaminomethyl-3,6-dimethylphenol whereas reaction occurs at the I-position using the classical procedures.
- Heaney, Harry,Papageorgiou, George,Wilkins, Robert F.
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p. 13361 - 13372
(2007/10/03)
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- The stereochemistry of organometallic compounds. XLIII* rhodium-catalysed reactions of 2-(alkenyloxy)benzylamines and 2-(N-allyl-N-benzylamino)benzylamine
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Reactions of 2-(allyloxy)benzylamines with H2/CO in the presence of rhodium catalysts give 1,3-benzoxazines, and 2-(N-allyl-N-benzylamino)benzylamine gives a quinazoline. These reactions have been shown to involve allylic cleavage followed by regioselective carbonylation at the internal carbon atom as demonstrated by crossover experiments. Reactions of longer chain (alkenyloxy)benzylamines under similar conditions give polymeric material.
- Campi, Eva M.,Jackson, W. Roy,McCubbin, Quentin J.,Trnacek, Andrew E.
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p. 219 - 230
(2007/10/03)
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- Allylic Rearrangements During the Rhodium-catalysed Reactions of 2-Allyloxybenzylamines and 2-(N-Allyl-N-benzylamino)benzylamine
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Reactions of 2-allyloxybenzylamines with H2/CO in the presence of rhodium catalysts give 1,3-benzoxazines via a reaction which involves allylic cleavage and carbonylation as demonstrated by crossover experiments.
- Campi, Eva M.,Jackson, W. Roy,McCubbin, Quentin J.,Trnacek, Andrew E.
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p. 2763 - 2764
(2007/10/02)
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- Method of producing monoclonal auto-anti-idiotypic antibodies
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This invention provides an auto-anti-idiotypic method for producing a monoclonal anti-idiotypic antibody. The method involves contacting lymphoid cells of an animal under suitable conditions with an effective antibody-raising amount of an antigen, collecting the lymphoid cells from the animal at a suitable time after the contacting and fusing the collected lymphoid cells with appropriate myeloma cells to produce a series of hybridoma cells each of which produces a monoclonal antibody. The method further involves screening, under suitable conditions, the series of hybridoma cells so produced to identify those which secrete a monoclonal antibody capable of binding to an antibody directed to the antigen, or to a receptor where the antigen is a ligand to the receptor, separately culturing a hybridoma cell so identified in an appropriate medium, and separately recovering under suitable conditions the monoclonal anti-idiotypic antibody produced by the hybridoma cell.
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- SELECTIVE FUNCTIONALIZATION OF AROMATIC COMPOUNDS. I. ORTHO-AMINOALKYLATION OF PHENOL AND o-tert-BUTYLPHENOL
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The aminomethylation of phenol in a complex with β-cyclodextrin, formalin, and dialkylamine gives the mono-ortho-aminoalkyl derivative.In contrast to this, for o-tert-butylphenol selective ortho-aminoalkylation can be realized without complex formation under the normal conditions of the Mannich reaction.
- Salakhutdinov, N. F.,Krysin, A. P.,Koptyug, V. A.
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p. 664 - 665
(2007/10/02)
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- THE EFFECT OF SULPHUR DIOXIDE ON THE MANNICH REACTIONS OF PHENOLS
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Regioselectivity in the ortho-dialkylaminomethylation of phenols in greatest, for example in reactions of 2,5-dimethylphenol, when a mixture of the phenol and sulphur dioxide is allowed to stand for several hours before the addition of a bis-(dialkylamino)methane (aminal) or an alkoxydialkylaminomethane (aminol ether).
- Fairhurst, Robin A.,Heaney, Harry,Papageorgiou, George,Wilkins, Robert F.
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p. 5801 - 5804
(2007/10/02)
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