- Oxidative Desymmetrization of Isoindolines Realized by tert -Butyl Nitrite (TBN) Initiated Radical sp 3C-H Activation Relay (CHAR)
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An oxidative desymmetrization of isoindolines was realized by TBN initiated radical sp 3C-H activation relay (CHAR), providing a series of ω-hydroxylactams in high yields. This reaction exhibits broad substrate scope and functional group tolerance, and even N -alkyl iso-indolines can be well tolerated. The mechanistic study shows that the C-H bond oxidation, dioxygen trapping and intramolecular 1,5-H shift might be the key steps to achieve the oxidative desymmetrization.
- Sun, Zheng,Shao, Yu,Zhang, Shuwei,Zhang, Yuxian,Yuan, Yu,Jia, Xiaodong
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p. 1663 - 1671
(2021/02/01)
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- Visible-Light-Mediated C(sp3)–H Thiocarbonylation for Thiolactam Preparation with Potassium Sulfide
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We report herein a protocol for thiolactam preparation with potassium sulfide via visible-light-mediated C(sp3)–H thiocarbonylation, in which polysulfide dianions and radical anions generated from potassium sulfide were the key active species. A variety of thiolactams were straightforward established under mild conditions. Moreover, it was successfully applied to structural modification of tetrahydroberberine.
- Tan, Wei,Wang, Cuihong,Jiang, Xuefeng
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supporting information
p. 1234 - 1238
(2019/11/21)
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- Iron-Catalysed Switchable Synthesis of Pyrrolidines vs Pyrrolidinones by Reductive Amination of Levulinic Acid Derivatives via Hydrosilylation
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A selective production of pyrrolidines vs pyrrolidinones via hydrosilylation of levulinic acid and levulinates by switching of the iron complex catalyst is presented herein. The reactions proceeded efficiently with various anilines and alkylamines under both visible light irradiation and thermal conditions with 43 examples in isolated yields up to 93%. Noticeably, under similar conditions, cyclic amines such as piperidines and azepanes were efficiently synthesized with yields up to 92%, by reaction of anilines with 1,5- or 1,6-keto acids, respectively. Similarly, N-arylinsolidoline compounds can be prepared from 2-formylbenzoic acid in 57–93% yields. (Figure presented.).
- Wei, Duo,Netkaew, Chakkrit,Darcel, Christophe
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supporting information
p. 1781 - 1786
(2019/02/26)
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- A class of GPR40 agonist compounds with amide structure, and uses thereof
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The present invention relates to a class of amide compounds with a novel structure, and a pharmaceutical composition thereof, wherein the structure of the amide compound is represented by a general formula (I). According to the present invention, the amide compound (I) can regulate GPR40 activity, and can be used for GPR40 activity related diseases such as diabetes and metabolic syndrome. The formula I is defined in the specification.
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Paragraph 0162; 0163; 0164
(2019/05/02)
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- Isoindolinone Synthesis: Selective Dioxane-Mediated Aerobic Oxidation of Isoindolines
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N-Alkyl and N-aryl-isoindolinones were prepared by a dioxane-mediated oxidation of isoindoline precursors. The transformation exhibits unique chemoselectivity for isoindonlines. A chiral tertiary (3°)-benzylic position was not racemized during oxidation, and methyl indoprofen was prepared by late stage oxidation. Mechanistic studies suggest a selective H atom transfer, which avoids many known oxidation (by-)products of isoindolinones.
- Thapa, Pawan,Corral, Esai,Sardar, Sinjinee,Pierce, Brad S.,Foss, Frank W.
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p. 1025 - 1034
(2019/01/24)
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- Tri(pentaflurophenyl)borane-catalyzed reduction of cyclic imides with hydrosilanes: Synthesis of pyrrolidines
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B(C6F5)3-catalyzed hydrosilylation of cyclic imides afforded an efficient synthetic method of pyrrolidines. In the presence of 5 mol% B(C6F5)3, various aromatic, aliphatic and polycyclic imides were smoothly reduced by PhSiH3 to generate the corresponding pyrrolidines in high yields. The reaction profiles monitored by 1H NMR spectroscopy disclosed the reduction process of cyclic imides and the effect of difference structure of the hydrosilanes on the hydrosilylation.
- Ding, Guangni,Wu, Xiaoyu,Lu, Bin,Lu, Wenkui,Zhang, Zhaoguo,Xie, Xiaomin
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p. 1144 - 1150
(2018/02/17)
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- Pyrrolidines compound and its synthesis method (by machine translation)
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A pyrrolidine compound and its synthetic method, will be dissolved in an organic solvent in the cyclic imide compound with hydrogen as a reducing agent of the reagent and a Lewis acid as a catalyst mixing, under the condition of refluxing to prepare the aromatic ring and fat ring pyrrolidines. Synthetic route of this invention is simple, efficient and economic, mild condition, wide applicability, to pyrrolidines compound at the later stage of industrial production will play a great role in promoting. (by machine translation)
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Paragraph 0020; 0021
(2017/08/28)
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- Reduction of Benzolactams to Isoindoles via an Alkoxide-Catalyzed Hydrosilylation
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An alkoxide-catalyzed reduction of benzolactams to isoindoles with silanes was realized. With t-BuOK as the catalyst and Ph2SiH2 as the reductant, a series of benzolactams containing different functional groups were reduced to the co
- Ding, Guangni,Wu, Xiaoyu,Jiang, Lili,Zhang, Zhaoguo,Xie, Xiaomin
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supporting information
p. 6048 - 6051
(2017/11/24)
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- Selective catalytic monoreduction of phthalimides and imidazolidine-2,4- diones
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Fluoride's new role: Selective and efficient monoreductions of imides can be achieved with polymethylhydrosiloxane (PMHS) and tetra-n-butylammonium fluoride (TBAF) as catalyst (see scheme). The system is characterized by good chemoselectivity, operational
- Das, Shoubhik,Addis, Daniele,Knoepke, Leif R.,Bentrup, Ursula,Junge, Kathrin,Brueckner, Angelika,Beller, Matthias
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supporting information; experimental part
p. 9180 - 9184
(2011/10/31)
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- 7-Azabicyclo[2.2.1]heptane as a structural motif to block mutagenicity of nitrosamines
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Nitrosamines are potent carcinogens and toxicants in the rat and potential genotoxins in humans. They are metabolically activated by hydroxylation at an α-carbon atom with respect to the nitrosoamino group, catalyzed by cytochrome P450. However, there has been little systematic investigation of the structure-mutagenic activity relationship of N-nitrosamines. Herein, we evaluated the mutagenicity of a series of 7-azabicyclo[2.2.1]heptane N-nitrosamines and related monocyclic nitrosamines by using the Ames assay. Our results show that the N-nitrosamine functionality embedded in the bicyclic 7-azabicylo[2.2.1]heptane structure lacks mutagenicity, that is, it is inert to α-hydroxylation, which is the trigger of mutagenic events. Further, the calculated α-C-H bond dissociation energies of the bicyclic nitrosamines are larger in magnitude than those of the corresponding monocyclic nitrosamines and N-nitrosodimethylamine by as much as 20-30 kcal/mol. These results are consistent with lower α-C-H bond reactivity of the bicyclic nitrosamines. Thus, the 7-azabicyclo[2.2.1]heptane structural motif may be useful for the design of nongenotoxic nitrosamine compounds with potential biological/medicinal applications.
- Ohwada, Tomohiko,Ishikawa, Satoko,Mine, Yusuke,Inami, Keiko,Yanagimoto, Takahiro,Karaki, Fumika,Kabasawa, Yoji,Otani, Yuko,Mochizuki, Masataka
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experimental part
p. 2726 - 2741
(2011/06/11)
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- An efficient method for the synthesis of 2, 3-dihydro-lH-isoindoles
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The synthesis of Af-substituted 2, 3-dihydro-lH-isoindoles from α, α'-dibromo-o-xylene and various primary amines in basic medium under ambient conditions is described. Especially the selection of 1, 4-dioxane as solvent and sodium hydroxide as suitable base to maintain the homogeneity of the medium are key steps to promote the reaction efficiently. Primary alkyl amines react faster as compared to their aromatic analogues under the conditions studied. Irrespective of the starting amine used, all the reactions proceed smoothly and provide 2, 3-dihydro-lH-isoindoles derivatives in excellent yields compared to hitherto known methods.
- Subbarayappa, Adimurthy,Patoliya, Paresh U.
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experimental part
p. 545 - 552
(2009/12/06)
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- Transnitrosation of thiols from aliphatic N-nitrosamines: S-nitrosation and indirect generation of nitric oxide
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S-Nitrosothiols and heme nitrosyl species are nitric oxide (NO)-derived metabolites that provide an endogenous reservoir of NO and also play roles in protein S-nitrosation, that is, transnitrosation of thiols (or thiolates) in proteins, thereby regulating protein functions and signal transduction pathways. Intriguingly, endogenous N-nitrosamines are present in similar abundance to S-nitrosothiols, and though they are thought to play similar physiological roles to S-nitrosothiols, their transnitrosation reactivities and their contribution to biological events are little understood. Herein we report aliphatic N-nitroso derivatives of 7-azabicyclo[2.2.1]heptanes, which do not act as NO donors themselves, but can transnitrosate thiols. On the basis of the calculated activation energies of transnitrosation and the aorta smooth-muscle relaxation activities of these N-nitrosamines, we present a possible scenario of S-transnitrosation from aliphatic N-nitrosamines, leading to indirect generation of NO. Copyright
- Yanagimoto, Takahiro,Toyota, Takeshi,Matsuki, Norio,Makino, Yumi,Uchiyama, Seiichi,Ohwada, Tomohiko
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p. 736 - 737
(2007/10/03)
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- An efficient synthesis of nitrogen heterocycles by Cp*Ir-catalyzed N-cycloalkylation of primary amines with diols
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A new efficient method for the N-cycloalkylation of primary amines with diols catalyzed by a Cp*Ir complex have been developed. A variety of five-, six-, and seven-membered cyclic amines are synthesized in good to excellent yields in environmentally benign and atom economical manner with the formation of only water as a coproduct. A large scale synthesis of N-benzylpiperidine and a two-step asymmetric synthesis of (S)-2-phenylpiperidine using (R)-1-phenylethylamine as a starting primary amine have been also achieved.
- Fujita, Ken-ichi,Fujii, Takeshi,Komatsubara, Atsuo,Enoki, Youichiro,Yamaguchi, Ryohei
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p. 673 - 682
(2008/09/18)
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- Cp*Ir complex-catalyzed N-heterocyclization of primary amines with diols: A new catalytic system for environmentally benign synthesis of cyclic amines
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(Chemical Equation Presented) A new efficient method for the N-heterocyclization of primary amines with diols catalyzed by a Cp*Ir complex was developed. A variety of five-, six-, and seven-membered cyclic amines were synthesized in good to excellent yields with the formation of only water as a byproduct. A two-step asymmetric synthesis of (S)-2-phenylpiperidine was also achieved using (R)-1-phenylethylamine as a starting primary amine.
- Fujita, Ken-Ichi,Fujii, Takeshi,Yamaguchi, Ryohei
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p. 3525 - 3528
(2007/10/03)
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- Synthesis, Characterization, and Thermolysis of 7-Amino-7-azabenzonorbornadienes
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Synthetic routes are given for the facile preparation of mono- and dibenzo-7-amino-7-azanorbornadienes 4 and 5.For 5 the key intermediate N-benzylisoindole (9) was treated with benzyne, generated via reaction of o-bromofluorobenzene with magnesium in THF to give tertiary amine 10.N-Bromosuccinimide-mediated debenzylation of 10 gave secondary amine 13, which was then aminated by O-(mesitylsulfonyl)hydroxylamine (MSH).Similarly amination of monobenzo amine 25 gave 4, which, however, proved to be unstable and therefore best isolated as the carbonyl (FMOC) derivative 27.Deblocking of 27 by means of diethylamine gave amine 4 as needed.Upon standing overnight in ether, free 4 underwent self-reduction to give dihydro derivative 29, whereas, in the presence of ethyl phenylpropiolate, cinnamate and dihydrocinnamate esters were formed.The simplest explanation for these results is that a reducing species is ejected upon thermolysis of 4.Nonstereospecific reduction occurred in contrast to the stereospecific reduction that occurred in the presence of authentic diimide precursor 23.Compounds 4 and 5 upon thermolysis in the presence of both acetic acid and propiolate ester led to stereospecific cis reduction.These results suggest that under acidic conditions protonated diimide is generated from both 4 and 5 whereas under neutral condotions 4 may yield azamine or a mixture of azamine and diimide.Direct involvement of 4 and 20 in reduction processes was, however, not eliminated.Thermolysis of 5 under neutral conditions is dependent on the solvent used.In DMF, clean conversion to 9,10-dihydroanthracene occurs whereas complex reaction mixtures are observed in benzene, chloroform, or THF.
- Carpino, Louis A.,Padykula, Robert E.,Barr, Donald E.,Hall, Frances H.,Krause, Josef G.,et al.
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p. 2565 - 2572
(2007/10/02)
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