- Base-Mediated Intramolecular Decarboxylative Synthesis of Alkylamines from Alkanoyloxycarbamates
-
A general and effective method for the synthesis of alkylamine via intramolecular decarboxylation of alkanoyloxycarbamates is described. The alkanoyloxycarbamates are readily prepared with alkyl carboxylic acids and hydroxylamine. The reaction shows a broad range of substrates (primary and secondary alkyl) with functional tolerance, and the corresponding products were obtained in good yields under mild conditions.
- Li, Peihe,Ma, Nuannuan,Wang, Zheng,Dai, Qipu,Hu, Changwen
-
p. 8233 - 8240
(2018/05/31)
-
- Fluorescent probe for identifying heavy metal copper ions and synthesis and application thereof
-
The invention relates to a ruthenium complex and a preparation method thereof and application. The specific structure of the ruthenium complex is as shown in general formula (I). The ruthenium complex can be used for detection of the copper ions. The ruthenium complex has quick specificity response to Cu2+, and an in vitro detection limit reaches 30 nmol.L; the ruthenium complex is good in biocompatibility and small in cytotoxicity and can be evenly distributed in whole cells, the Cu2+ level in the cells can be detected; and the content and distribution of in vivo Cu2+ can be monitored in real time.
- -
-
Paragraph 0042-0045
(2017/11/18)
-
- PROCESS FOR THE CATALYTIC DIRECTED CLEAVAGE OF AMIDE-CONTAINING COMPOUNDS
-
The present invention relates to a catalytic method for the conversion of amide-containing compouds by means of a build-in directing group and upon the action of a heteronucleophilic compound (in se an amine (RNH2 or RNHR') or an alcohol (ROH) or a thiol (RSH)) in the presence of a metal catalyst to respectively esters, thioesters, carbonates, thiocarbonates and to what is defined as amide-containing compounds (such as carboxamides, urea, carbamates, thiocarbamates). The present invention also relates to these amide-containing compounds having a build-in directing group (DG), as well as the use of such directing groups in the catalytic directed cleavage of N-DG amides with the use of heteronucleophiles (in se an amine (RNH2 or RNHR') or an alcohol (ROH) or thiol (RSH)).
- -
-
Page/Page column 60; 61
(2017/04/11)
-
- Efficient and expeditious chemoselective BOC protection of amines in catalyst and solvent-free media
-
A green and eco-friendly route for the almost quantitative BOC protection of a large variety of aliphatic and aromatic amines, amino acids, and amino alcohols is reported in catalyst and solvent-free media under mild reaction conditions. The products were confirmed by 1H, 13C NMR, IR spectroscopy, and in some cases, elemental analysis. This protocol does not require any water quenches, solvent separations, and purification steps, such as recrystallization and column chromatography.
- Viswanadham, Balaga,Mahomed, Abdul S.,Friedrich, Holger B.,Singh, Sooboo
-
p. 1355 - 1363
(2017/02/15)
-
- Alpha-oxidation of amine derivatives by bis(2,2,2-tri-chloroethyl) azodicarboxylate and application of its products as iminium ion equivalents
-
Alpha-oxidation of amine derivatives by azodicarboxylate was examined. Among several azodicarboxylate esters and amides tested, bis(2,2,2-trichloroethyl) azodicarboxylate, that has highly electrophilic 2,2,2-trichloroethoxycarbonyl functional groups, was found to have excellent oxidation reactivity. Acylated or carbamoylated amines were suitable substrates for this reaction condition. Tertially amines could react in the same manner, but spontaneous elimination of hydrazinyl group occurred to give dimerized products. The reaction products were found to react with nucleophiles in the presence of Lewis or Br?nsted acid catalyst. This strongly suggests that the reaction products, alpha-hydrazinated amine derivatives, might serve as carbonyl group equivalents, very useful intermediates in synthetic organic chemistry.
- Honzawa, Shinobu,Uchida, Mitsuaki,Tashiro, Takuya,Sugihara, Takumichi
-
p. 994 - 1029
(2017/07/27)
-
- A simple, rapid, and efficient N-Boc protection of amines under ultrasound irradiation and catalyst-free conditions
-
A green and simple approach for the N-Boc protection on structurally diverse amines under ultrasound irradiation is described. Selective N-Boc protection was achieved in excellent isolated yield in a short reaction time at room temperature. Mild conditions, inexpensive and an easily available reagent, and absence of any auxiliary substances are the main advantages of this procedure. Graphical abstract: [Figure not available: see fulltext.]
- Amira, Aicha,K'Tir, Hacene,Berredjem, Malika,Aouf, Nour-Eddine
-
p. 509 - 515
(2014/03/21)
-
- Hydrogen-free alkene reduction in continuous flow
-
The first continuous hydrogenation that requires neither H2 nor metal catalysis generates diimide by a novel reagent combination. The simple flow reactor employed minimizes residence time by enabling safe operation at elevated temperature.
- Kleinke, Andrew S.,Jamison, Timothy F.
-
supporting information
p. 710 - 713
(2013/03/29)
-
- Replacing conventional carbon nucleophiles with electrophiles: Nickel-catalyzed reductive alkylation of aryl bromides and chlorides
-
A general method is presented for the synthesis of alkylated arenes by the chemoselective combination of two electrophilic carbons. Under the optimized conditions, a variety of aryl and vinyl bromides are reductively coupled with alkyl bromides in high yields. Under similar conditions, activated aryl chlorides can also be coupled with bromoalkanes. The protocols are highly functional-group tolerant (-OH, -NHTs, -OAc, -OTs, -OTf, -COMe, -NHBoc, -NHCbz, -CN, -SO2Me), and the reactions are assembled on the benchtop with no special precautions to exclude air or moisture. The reaction displays different chemoselectivity than conventional cross-coupling reactions, such as the Suzuki-Miyaura, Stille, and Hiyama-Denmark reactions. Substrates bearing both an electrophilic and nucleophilic carbon result in selective coupling at the electrophilic carbon (R-X) and no reaction at the nucleophilic carbon (R-[M]) for organoboron (-Bpin), organotin (-SnMe3), and organosilicon (-SiMe2OH) containing organic halides (X-R-[M]). A Hammett study showed a linear correlation of σ and σ(-) parameters with the relative rate of reaction of substituted aryl bromides with bromoalkanes. The small ρ values for these correlations (1.2-1.7) indicate that oxidative addition of the bromoarene is not the turnover-frequency determining step. The rate of reaction has a positive dependence on the concentration of alkyl bromide and catalyst, no dependence upon the amount of zinc (reducing agent), and an inverse dependence upon aryl halide concentration. These results and studies with an organic reductant (TDAE) argue against the intermediacy of organozinc reagents.
- Everson, Daniel A.,Jones, Brittany A.,Weix, Daniel J.
-
supporting information; experimental part
p. 6146 - 6159
(2012/05/07)
-
- A generic approach for the catalytic reduction of nitriles
-
The scope of nickel boride mediated reduction of nitriles has been extended further to allow the preparation of Boc protected amines via a mild catalytic process. It is noteworthy that the toxicity of this procedure is greatly reduced due to its catalytic
- Caddick, Stephen,Judd, Duncan B.,Lewis, Alexandra K. De K.,Reich, Melanie T.,Williams, Meredith R. V.
-
p. 5417 - 5423
(2007/10/03)
-
- Ultrasound promoted 'one pot' conversion of nitrocompounds to carbamates
-
An efficient ultrasound promoted novel direct conversion of nitro compounds to N-(tert-butoxycarbonyl) amines and N-(ethoxycarbonylamines) is achieved using Sn-NH4Cl for the first time.
- Chandrasekhar,Narsihmulu,Jagadeshwar
-
p. 771 - 772
(2007/10/03)
-
- Reductive BOC-amination of aldehydes
-
Base-assisted elimination-reduction of α-amidoalkyl sulfones with sodium borohydride proceeds in tetrahydrofuran at room temperature leading to the corresponding BOC-amines in good yields.
- Bernacka, Elbieta,Klepacz, Anna,Zwierzak, Andrzej
-
p. 5093 - 5094
(2007/10/03)
-
- Convenient synthesis of protected primary amines form nitriles
-
Investigations into the use of nickel chloride and sodium borohydride for the reduction of nitriles showed the secondary amine dimers to be the major products under normal conditions. The addition of a suitable trapping agent, such as di-tert-butyl dicarbonate, allowed the isolation of the protected primary amines. (C) 2000 Elsevier Science Ltd.
- Caddick, Stephen,De K. Haynes, Alexandra K.,Judd, Duncan B.,Williams, Meredith R.V.
-
p. 3513 - 3516
(2007/10/03)
-
- Studies on the reactivity of α-cyano-α-isocyanoalkanoates - Versatile synthons for the assembly of imidazoles
-
The reactivity and the synthetic potential of α-cyano-α- isocyanoalkanoates 2 were investigated. Interestingly, reaction of 2 with alkoxides gave (alkoxy)(alkyl)imidazoles 5, whereas the analogous thiolates led to different products, namely substituted 4H-imidazoles 7, together with compounds 6, which formed by addition of thiolate to the isocyano group. Primary amines reacted, on one hand, in the same manner as thiolates to form of 4H-imidazoles 10, and, on the other hand, cleavage of the molecule to the proposed unstable aminoimidazole 8 and the carbamate 9 was observed. Secondary amines add selectively to the isocyano group to form compounds 11. Like simple isocyanides, α-cyano-α-isocyanoalkanoates 2 can be subjected to [4+1] cycloadditions and multicomponent reactions of the Passerini type. Mechanisms for the described reactions are discussed.
- Bergemann, Marco,Neidlein, Richard
-
p. 909 - 918
(2007/10/03)
-
- Protection of a protecting group: Preparation of stable N-silylated t-butyl carbamates
-
The practical preparation of N-silylated carbamates (typified by 1) is reported. These compounds are synthesized in high yields by treating N-t-Boc-protected primary amines with silyl triflate reagents in dichloromethane in the presence of triethylamine.
- Roby, Johanne,Voyer, Normand
-
p. 191 - 194
(2007/10/03)
-
- A convenient and general synthesis of alkylcarbamates from tertiary isocyanates and alcohols
-
Reaction of primary, secondary and tertiary alkyl isocyanates with benzyl alcohol, tert-butyl alcohol or 1-adamantanol in the presence of 5% hydrogen chloride provides a mild and convenient method for alkyl alkylcarbamate synthesis.
- Benalil,Roby,Carboni,Vaultier
-
p. 787 - 788
(2007/10/02)
-
- A New Method for the Synthesis of Amides from Amines: Ruthenium Tetroxide Oxidation of N-Protected Alkylamines
-
A simple synthetic method for the preparation of amides from the corresponding primary alkylamines was elaborated using ruthenium tetroxide (RuO4) oxidation as a key step.
- Tanaka, Ken-Ichi,Yoshifuji, Shigeyuki,Nitta, Yoshihiro
-
p. 3125 - 3129
(2007/10/02)
-
- New Amino-protective Reagents for t-Butoxycarbonylation and Benzyloxycarbonylation of Amines and Amino Acids
-
New amino-protective reagents for t-butoxycarbonylation and benzyloxycarbonylation of amines and amino acids have been developed. t-Butyl 2-pyridyl carbonate and t-butyl S-(2-pyridyl) thiocarbonate react cleanly with various amines and amino acids to afford N-Boc amines and N-Boc amino acids in high yields.Benzyl 2-pyridyl carbonate and O-benzyl S-(2-pyridyl) thiocarbonate are also found to be very effective in the benzyloxycarbonylation of amino acids.
- Kim, Sunggak,Lee, Jae In,Yi, Kyu Yang
-
p. 3570 - 3575
(2007/10/02)
-