- Rh(II)-mediated one-pot synthesis of dihydrobenzofuran and spiro[2.5]oct-1-ene: Experimental and DFT studies
-
This study represents an experimental and computational approach to investigate the rhodium-catalyzed one-pot synthesis of dihydrobenzofuran-4-one (DBF) and spiro[2.5]oct-1-ene (SOE) derivatives. Density functional theory (DFT) calculations were performed at B3LYP and M06-2X level theory. For mechanistic studies, the calculation employing B3LYP/GenECP/LanL2DZ/6-311++G(d,p) level of theory demonstrated that a [3 + 2] cycloaddition reaction between diazo compound and phenylacetylene (PhA) proceeds through a two-step mechanism via a barrierless and highly exergonic process with relative free energy 73.61 kcal/mol to yield the kinetically favored DBF derivatives (50%–62.5%). In contrast, the assemble of SOE derivatives follows [2 + 1] cycloaddition between in situ generated cyclohexane-1,3-dione carbene-2 and PhA, with the potential energy barrier 4.41 kJ/mol. Thermochemistry calculation disclosed that the cycloaddition reactions are spontaneous, and DBF (6a) is thermodynamically more stable than its constitutional isomer SOE (7a) by 42.59 kcal/mol. However, natural bond orbital (NBO), HOMO–LUMO energy gaps (4.62–4.89 eV), dipole moments, polarizability, first-order hyperpolarizability, and global reactivity descriptors were calculated to understand products' structural features. Additionally, Merck Molecular Force Field (MMFF94), followed by the B3LYP level of theory, was applied to predict the relative stability for the various conformations of 6b and 7b. The Boltzmann weighted average 1H chemical shift computed by GIAO-B3LYP/6-311+(2d,p) method and UV-Vis absorption calculated using time-dependent density functional theory (TD-DFT) agree with experimental results. Finally, the synthesis of DBF and SOE derivatives is herein illustrated.
- Hoque, Mohammad Mazharol,Bari, Md. Abdul,Khan, Md. Wahab
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- Development of prohibitin ligands against osteoporosis
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Current therapeutic approaches to osteoporosis display some potential adverse effects and a limited efficacy on non-vertebral fracture reduction. Some sulfonylamidines targeting the scaffold proteins prohibitins-1 and 2 (PHB1/2) have been showed to inhibit the formation of osteoclasts in charge of bone resorption. Herein, we report the development of a second generation of anti-osteoclastic PHB ligands. The most potent compound, IN45, showed 88% inhibition at the low concentration of 5 μM, indicates that it might serve as a basis for the development of new antiosteoporotic drugs.
- Tabti, Redouane,Lamoureux, Fran?ois,Charrier, Céline,Ory, Benjamin,Heymann, Dominique,Bentouhami, Embarek,Désaubry, Laurent
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supporting information
(2020/11/04)
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- Formal Allylation and Enantioselective Cyclopropanation of Donor/Acceptor Rhodium(II) Azavinyl Carbenes
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A highly efficient formal allylation of dihydronaphthotriazoles with alkenes under rhodium(II) catalysis is reported. Various allyl dihydronaphthalene derivatives were furnished via rhodium(II) azavinyl carbenes with moderate to good yields and excellent chemoselectivity. When monosubstituted alkenes are used, cyclopropanation occurs and good to excellent enantioselectivities have been achieved. Particularly noteworthy is the allylic C(sp2)-H activation instead of traditional C(sp3)-H activation in the formal allylation process.
- Liu, Zhili,Chen, Lianfen,Zhu, Dong,Zhu, Shifa
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supporting information
p. 1275 - 1279
(2021/02/20)
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- Taking diazo transfer to water: α-diazo carbonyl compounds from in situ generated mesyl azide
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Mesyl azide generated in situ in aqueous medium converted a range of active methylene substrates into the corresponding diazo compounds in good yields and high purity with no need for chromatographic purification. The products thus obtained are suitable for the subsequent RhII-catalyzed O–H insertions with no need for chromatography in the interim.
- Dar'in, Dmitry V.,Krasavin, Mikhail,Shevalev, Robert M.,Zhmurov, Petr A.
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p. 372 - 373
(2020/06/19)
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- A Base-Controlled Reaction of 2-Cyanoacetamidines (3,3-Diaminoacrylonitriles) with Sulfonyl Azides as a Route to Nonaromatic 4-Methylene-1,2,3-triazole-5-imines
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Reactions of 2-cyanoacetamidines with sulfonyl azides were shown to take place via two different pathways to form a mixture of 1-substituted 5-amino-1,2,3-triazoles 3 and novel 4-methylene-1H-1,2,3-triazole-5(4H)-imine derivatives 4–14. In the absence of
- Silaichev, Pavel S.,Beryozkina, Tetyana V.,Novikov, Mikhail S.,Dehaen, Wim,Bakulev, Vasiliy A.
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p. 3688 - 3698
(2020/06/09)
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- One-Pot Copper-Catalyzed Three-Component Reaction of Sulfonyl Azides, Alkynes, and Allylamines to Access 2,3-Dihydro-1 H-imi-dazo[1,2-a]indoles
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A copper-catalyzed multicomponent reaction of sulfonyl azides, alkynes, and allylamines affording 2,3-dihydro-1 H-imidazo-[1,2-a]indoles in moderate yields is reported. Four C-N bonds are constructed- by way of azide-alkyne cycloaddition (CuAAC) and double Ullmann-type coupling reactions in a one-pot process.
- Jin, Hongwei,Liu, Daohong,Liu, Yunkui,Zhou, Bingwei
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supporting information
p. 1417 - 1424
(2020/04/27)
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- One-pot synthesis of sulfonyl-1H-1,2,3-triazolyl-thiomorpholine 1,1-dioxide derivatives and evaluation of their biological activity
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A one-pot procedure for the synthesis of novel 1,2,3-triazole derivatives (5a–5l) in good yields (63 to 77%) using different sulfonic acids and 4-(prop-2-yn-1-yl)thiomorpholine 1,1-dioxide through the in situ generated sulfonyl azides was developed. The structures of the newly synthesized compounds were confirmed by 1H NMR, 13C NMR, mass spectrometry, and elemental analysis. The newly synthesized compounds were screened for in?vitro antibacterial activity and free radical scavenging activity in terms of hydrogen donating or radical scavenging ability by the DPPH method. Among all, the compound N-(4-((4-((1,1-dioxidothiomorpholino) methyl)-1H-1,2,3-triazol-1-yl)sulfonyl)phenyl) acetamide (5l) was found to exhibit potent activity as compared to the standard drugs.
- Sreerama, Rakesh,Narasimha Swamy,Ravinder,Vasudeva Reddy,Narsimha, Sirassu
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p. 455 - 460
(2020/12/17)
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- Ligand-Free, Quinoline N-Assisted Copper-Catalyzed Nitrene Transfer Reaction to Synthesize 8-Quinolylsulfimides
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An efficient copper-catalyzed, quinolyl N-directed nitrene transfer reaction to 8-quinolylsulfides was described. A variety of 8-quinolylsulfimides with different functional groups were synthesized in moderate to high yields. The obtained 8-quinolylsulfimides were proved to be promising novel type of bidentate ligands in Pd(II)-catalyzed allylic alkylation.
- Xiao, Xinsheng,Huang, Sanping,Tang, Shanshan,Jia, Guokai,Ou, Guangchuan,Li, Yangyan
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p. 7618 - 7629
(2019/06/27)
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- Mechanistic Study of In Situ Generation and Use of Methanesulfonyl Azide as a Diazo Transfer Reagent with Real-Time Monitoring by FlowNMR
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The mechanistic pathway by which the hazardous diazo transfer reagent methanesulfonyl azide can be formed in situ, from methanesulfonyl chloride and aqueous sodium azide, has been investigated using real-time reaction monitoring by FlowNMR. In the presence of triethylamine, rapid generation of methanesufonyl azide is observed, via a mechanistic pathway consistent with involvement of a sulfene or methanesulfonyl triethylammonium intermediate. Accordingly, it is possible to generate and use methanesulfonyl azide in a single synthetic step for a diazo transfer process.
- Lynch, Denis,O'Mahony, Rosella M.,McCarthy, Daniel G.,Bateman, Lorraine M.,Collins, Stuart G.,Maguire, Anita R.
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supporting information
p. 3575 - 3580
(2019/06/08)
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- C-H alkenylation/cyclization and sulfamidation of 2-phenylisatogens using: N -oxide as a directing group
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The first example of transition-metal-catalyzed C-H activations of 2-phenylisatogens with alkynes and sulfonyl azides has been developed using N-oxide as the directing group. Ru(ii)-Catalyzed C-H alkenylation/cyclization and Ir(iii)-catalyzed direct C-H sulfamidation proceeded with good yields and excellent functional group tolerance. Importantly, these two transformations provided straightforward routes for the synthesis of indol-3-one derivatives and sulfamidated 2-phenylisatogens respectively, which might be of considerable bioactivities.
- Guo, Lingmei,Tang, Baolan,Nie, Ruifang,Liu, Yanzhao,Lv, Shan,Wang, Huijing,Guo, Li,Hai, Li,Wu, Yong
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supporting information
p. 10623 - 10626
(2019/09/06)
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- Ru(II)-catalyzed α-sulfonamidation of cyclic β-ketoesters with sulfonyl azides
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α-Sulfonamidation of β-ketoesters with sulfonyl azide has been developed for the first time using a catalytic amount of Ru(II) complex to produce the 1-oxo-2-(sulfonamido)-2,3-dihydro-1H-indene-2-carboxylate and 1-oxo-2-(sulfonamido)-1,2,3,4-tetrahydronaphthalene-2-carboxylate derivatives in good yields. This method also works well with α-iodotetralones to afford the N-(1,4-dioxo-1,4-dihydronaphthalen-2-yl)sulphonamide derivatives under similar conditions.
- Rao, M.V. Krishna,Reddy, K. Nagarjuna,Sridhar,Reddy, B.V. Subba
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supporting information
(2019/09/16)
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- Water/Alkali-Catalyzed Reactions of Azides with 2-Cyanothioacetamides. Eco-Friendly Synthesis of Monocyclic and Bicyclic 1,2,3-Thiadiazole-4-carbimidamides and 5-Amino-1,2,3-triazole-4-carbothioamides
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The reactions of thioamides with azides in water were studied. It was reliably shown that the reaction of 2-cyanothioacetamides 1 with various types of azides 2 in water in the presence of alkali presents an efficient, general, one-step, atom-economic, and eco-friendly method for the synthesis of 1,2,3-thiadiazol-4-carbimidamides 5 and 1,2,3-triazole-4-carbothioamides 4. This method can be extended to the one-pot reaction of sulfonyl chlorides and 6-chloropyrimidines 2′o with sodium azide, leading to final products in higher yields, that is, avoiding the isolation of unsafe sulfonyl azides. The method was furthermore applied to the reaction of N,N′-bis-(2-cyanothiocarbonyl)pyrazine 1h with sulfonyl azides to afford bicyclic 1,2,3-thiadiazoles 8 and 1,2,3-triazoles 9 connected via a 1,1′-piperazinyl linker. 2-Cyanothioacetamides 1 were also shown to react with aromatic azides in water in the presence of alkali to afford 1-aryl-5-amino-1,2,3-triazole-4-carbothioamides 11. In contrast to aromatic azides and similarly to sulfonyl azides, 6-azidopyrimidine-2,4-diones 2o-q react with cyanothioacetamides to form N-pyrimidin-6-yl-5-dialkylamino-1,2,3-thiadiazole-4-N-l-carbimidamides 12. A mechanism was proposed to rationalize the role of water in changing the reactivity of azides toward 2-cyanothioacetamides.
- Filimonov, Valeriy O.,Dianova, Lidia N.,Beryozkina, Tetyana V.,Mazur, Dmitrii,Beliaev, Nikolai A.,Volkova, Natalia N.,Ilkin, Vladimir G.,Dehaen, Wim,Lebedev, Albert T.,Bakulev, Vasiliy A.
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p. 13430 - 13446
(2019/10/16)
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- Iridium(III)-Catalyzed Regiocontrolled Direct Amidation of Isoquinolones and Pyridones
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Iridium(III)-catalyzed highly regiocontrolled C3/C8 amidation of isoquinolones and C6 amidation of 2-pyridones has been successfully accomplished with various azides. The optimized method is operationally simple with a broad substrate scope. The protocol has been found to be scalable. (Figure presented.).
- Das, Debapratim,Samanta, Rajarshi
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supporting information
p. 379 - 384
(2017/12/26)
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- Iridium(III)-Catalyzed Selective and Mild C-H Amidation of Cyclic N-Sulfonyl Ketimines with Organic Azides
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A general protocol for iridium catalyzed direct C?H amidation of cyclic N-sulfonyl ketimines using sulfonyl, acyl and aryl azides as nitrogen source is reported herein. The reaction takes place at room temperature with acyl and aryl azides, while an elevated temperature needed with sulfonyl azides to furnish aminated sultams in excellent yields with complete chemo and regioselectivity, thus providing a robust and environmentally benign process to the synthesis of aminosultams. (Figure presented.).
- Maraswami, Manikantha,Chen, Gang,Loh, Teck-Peng
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supporting information
p. 416 - 421
(2017/11/13)
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- A copper-catalyzed three component reaction of aryl acetylene, sulfonyl azide and enaminone to form iminolactone via 6π electrocyclization
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We developed a copper-catalyzed three component reaction of aryl acetylene, enaminone and sulfonyl azide to construct iminolactone via a cascade process involving copper-catalyzed alkyne-azide cycloaddition (CuAAC), Michael addition of metalated ketenimin
- Sun, Jiarui,Cheng, Xiangsheng,Mansaray, John Kamanda,Fei, Weihong,Wan, Jieping,Yao, Weijun
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supporting information
p. 13953 - 13956
(2019/01/03)
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- Copper-Catalyzed Carbenoid Insertion Reactions of α-Diazoesters and α-Diazoketones into Si-H and S-H Bonds
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An efficient copper-catalyzed carbenoid insertion reaction of α-diazo carbonyl compounds into Si-H and S-H bonds was developed. A wide range of α-silylesters and α-thioesters was obtained in high yields (up to 98%) from α-diazoesters using 5 mol% of a simple copper(I) salt as catalyst. Using 0.05 mol% of the same catalyst, α-diazoketones led to α-silylketones in low to good yields (up to 70%).
- Keipour, Hoda,Jalba, Angela,Delage-Laurin, Léo,Ollevier, Thierry
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p. 3000 - 3010
(2017/03/23)
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- Exploiting the Continuous in situ Generation of Mesyl Azide for Use in a Telescoped Process
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The hazardous diazo transfer reagent mesyl azide has been safely generated and used in situ for continuous diazo transfer as part of an integrated synthetic process with an embedded safety quench. Diazo transfer to β-keto esters and a β-ketosulfone was successful. In-line phase separation, by means of a continuous liquid–liquid separator, enabled direct telescoping with a thermal Wolff rearrangement.
- O'Mahony, Rosella M.,Lynch, Denis,Hayes, Hannah L. D.,Ní Thuama, Eilís,Donnellan, Philip,Jones, Roderick C.,Glennon, Brian,Collins, Stuart G.,Maguire, Anita R.
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p. 6533 - 6539
(2017/10/24)
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- DABCO/AcOH Jointly Accelerated Copper(I)-Catalysed Cycloaddition of Azides and Alkynes on Water at Room Temperature
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An expeditious room temperature protocol for the synthesis of 1,4-disubstituted 1,2,3-triazoles from terminal alkynes and substituted azides has been achieved using the combination of CuSO4-ascorbate/1,4-diazabicyclo[2.2.2]octane/acetic acid. This expeditious protocol is applicable to aryl, alkyl, and sulfonyl azides. Acetic acid accelerates the protonation of cuprated triazole and thus avoids the possible side reactions. Devoid of acetic acid, the reaction pathway alters to the ketinimine route and results in the formation of sulfonamides.
- Sarode, Prashant B.,Bahekar, Sandeep P.,Chandak, Hemant S.
-
supporting information
p. 2681 - 2684
(2016/11/26)
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- Product-Derived Bimetallic Palladium Complex Catalyzes Direct Carbonylation of Sulfonylazides
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A novel product-derived bimetallic palladium complex catalyzes a sulfonylazide-transfer reaction with the σ-donor/π-acceptor ligand CO, and is advantageous given its broad substrate scope, high efficiency, and mild reaction conditions (atmospheric pressure of CO at room temperature). This methodology provides a new approach to sulfonylureas, which are present in both pharmaceuticals and agrochemicals. The synthesis of Glibenclamide on a gram scale further revealed the practical utility of this procedure. Mechanistically, the generation of a bridged bimetallic palladium species derived from the product sulfonylurea is disclosed as the crucial step for this catalytic cycle.
- Zhao, Jin,Li, Zongyang,Song, Shaole,Wang, Ming-An,Fu, Bin,Zhang, Zhenhua
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supporting information
p. 5545 - 5549
(2016/05/09)
-
- A Direct Access to 7-Aminoindoles via Iridium-Catalyzed Mild C-H Amidation of N-Pivaloylindoles with Organic Azides
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Ir(III)-catalyzed regioselective direct C-7 amidation of indoles in reaction with organic azides has been developed. While its efficiency was varied by the choice of N-directing groups, N-pivaloylindoles were most effective in undergoing the desired amidation at room temperature over a broad range of substrates. The reaction was scalable, and deprotection of the chelation group was also facile.
- Kim, Youyoung,Park, Juhyeon,Chang, Sukbok
-
supporting information
p. 1892 - 1895
(2016/05/19)
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- N-Sulfonyl amidine synthesis via three-component coupling reaction using heterogeneous copper catalyst derived from metal-organic frameworks
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Three-component coupling reaction of terminal alkyne, sulfonyl azide, and amine for the synthesis of N-sulfonyl amidine was developed using heterogeneous Cu@C catalyst, which was generated by pyrolysis of HKUST-1 (Cu3(BTC)2, BTC?=?1,
- Kim, Myeong Jin,Kim, Bo Ram,Lee, Chang Yeon,Kim, Jinho
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supporting information
p. 4070 - 4073
(2016/08/18)
-
- Direct C-H amidation of benzoic acids to introduce meta- and para-amino groups by tandem decarboxylation
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The Ir-catalyzed mild C-H amidation of benzoic acids with sulfonyl azides was developed to give reactions with high efficiency and functional-group compatibility. Subsequent protodecarboxylation of ortho-amidated benzoic acid products afforded meta- or para-substituted (N-sulfonyl)aniline derivatives, the latter being inaccessible by other C-H functionalization approaches. The decarboxylation step was compatible with the amidation conditions, enabling a convenient one-pot, two-step process. Without a trace: Carboxylic acids are used as traceless directing groups in the Ir-catalyzed direct C-H amidation of arenes with sulfonyl azides under mild conditions. The tandem protodecarboxylation of the ortho-amidated benzoic acid products afforded meta- or para-substituted (N-sulfonyl)anilines, which are difficult to obtain by other C-H functionalization approaches.
- Lee, Donggun,Chang, Sukbok
-
supporting information
p. 5364 - 5368
(2015/03/30)
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- Iridium-catalyzed direct ortho-C-H amidation of benzoic acids with sulfonylazides
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A mild and efficient iridium-catalyzed ortho-C-H amidation with sulfonyl azides by weakly coordinating carboxylic acid was demonstrated, which provided a novel approach to anthranilic acid derivatives.
- Wei, Ming-E,Wang, Lian-Hui,Li, Yu-Dong,Cui, Xiu-Ling
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supporting information
p. 1336 - 1340
(2015/10/28)
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- Preparation of triazoloindoles via tandem copper catalysis and their utility as α-imino rhodium carbene precursors
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3-Sulfonyl[1,2,3]triazolo[4,5-b]indoles were efficiently prepared via a tandem catalysis process involving intramolecular ligand stabilized CuAAC and Cu-catalyzed C-N coupling. The obtained 3-sulfonyl[1,2,3]triazolo[4,5-b]indoles could be utilized as α-im
- Xing, Yanpeng,Sheng, Guorong,Wang, Jing,Lu, Ping,Wang, Yanguang
-
supporting information
p. 1244 - 1247
(2014/03/21)
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- Copper-catalyzed three-component synthesis of 3-Aminopyrazoles and 4-iminopyrimidines via β-alkynyl-N-sulfonyl ketenimine intermediates
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3-Aminopyrazoles and 4-iminopyrimidines were efficiently prepared via copper-catalyzed three-component reactions of butadiynes, sulfonylazides, and hydrazides or imidamides. The reactions were regioselectively approached via the formation of a β-alkynyl-N-sulfonyl ketenimine intermediate which represented a new and effective 1,3-dielectrophilic equivalent in organic synthesis.
- Xing, Yanpeng,Cheng, Binyu,Wang, Jing,Lu, Ping,Wang, Yanguang
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supporting information
p. 4814 - 4817
(2015/04/27)
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- Iridium-catalyzed direct C-H amidation with weakly coordinating carbonyl directing groups under mild conditions
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An iridium-catalyzed direct C-H amidation of weakly coordinating substrates, in particular of those bearing ester and ketone groups, under very mild conditions has been developed. The observed high reaction efficiency was achieved by the combined use of acetic acid and lithium carbonate as additives. Copyright
- Kim, Jinwoo,Chang, Sukbok
-
supporting information
p. 2203 - 2207
(2014/03/21)
-
- Iridium-catalyzed intermolecular amidation of sp3 C-H bonds: Late-stage functionalization of an unactivated methyl group
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Reported herein is the iridium-catalyzed direct amidation of unactivated sp3 C-H bonds. With sulfonyl and acyl azides as the amino source, the amidation occurs efficiently under mild conditions over a wide range of unactivated methyl groups with high functional group tolerance. This procedure can be successfully applied for the direct introduction of an amino group into complex compounds and thus can serve as a powerful synthetic tool for late-stage C-H functionalization.
- Kang, Taek,Kim, Youngchan,Lee, Donggun,Wang, Zhen,Chang, Sukbok
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supporting information
p. 4141 - 4144
(2014/04/03)
-
- Synthesis of 2-Aryl-2 H-benzotrizoles from azobenzenes and N-sulfonyl azides through sequential rhodium-catalyzed amidation and oxidation in one pot
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An efficient synthetic method of 2-aryl-2H-benzotriazoles from nonprefunctionalized azobenzenes and N-sulfonyl azides via sequential Rh-catalyzed amidation (C-N bond formation) and oxidation (N-N bond formation) with PhI(OAc)2 in one pot is reported.
- Ryu, Taekyu,Min, Jiae,Choi, Wonseok,Jeon, Woo Hyung,Lee, Phil Ho
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supporting information
p. 2810 - 2813
(2014/06/23)
-
- Regioselective introduction of heteroatoms at the C-8 position of quinoline N-oxides: Remote C-H activation using N-oxide as a stepping stone
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Reported herein is the metal-catalyzed regioselective C-H functionalization of quinoline N-oxides at the 8-position: direct iodination and amidation were developed using rhodium and iridium catalytic systems, respectively. Mechanistic study of the amidation revealed that the unique regioselectivity is achieved through the smooth formation of N-oxide-chelated iridacycle and that an acid additive plays a key role in the rate-determining protodemetalation step. While this approach of remote C-H activation using N-oxide as a directing group could readily be applied to a wide range of heterocyclic substrates under mild conditions with high functional group tolerance, an efficient synthesis of zinquin ester (a fluorescent zinc indicator) was demonstrated.
- Hwang, Heejun,Kim, Jinwoo,Jeong, Jisu,Chang, Sukbok
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supporting information
p. 10770 - 10776
(2014/08/18)
-
- Synthesis of 1,2-amino alcohols via catalytic C-H amidation of sp3 methyl C-H bonds
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Herein a new synthetic route to 1,2-amino alcohols is presented by using C-H amidation of sp3 methyl C-H bonds as a key step. Readily available alcohols were employed as starting materials after converting them to removable ketoxime chelating g
- Kang, Taek,Kim, Heejeong,Kim, Jeung Gon,Chang, Sukbok
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supporting information
p. 12073 - 12075
(2014/12/11)
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- Direct synthesis of sulfonyl azides from sulfonic acids
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A one-pot process for the synthesis of various sulfonyl azides (RSO2N3) by treating sulfonic acids with triphenylphosphine/trichloroisocyanuric acid/sodium azide at room temperature is described. A wide range of arenesulfonyl and alkanesulfonyl azides was obtained in excellent yields under mild conditions.
- Kiani, Adeleh,Akhlaghinia, Batool,Rouhi-Saadabad, Hamed,Bakavoli, Mehdi
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p. 119 - 127
(2014/01/23)
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- Synthesis and charge-carrier transport properties of poly(phosphole p-alkanesulfonylimide)s
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A new class of polyphospholes bearing alkanesulfonylimino moieties on the phosphorus(V) centers was prepared by the Pd-CuI-promoted Stille coupling reaction to investigate the charge-carrier transport properties of the π-networks of polyphospholes. Time-o
- Matano, Yoshihiro,Ohkubo, Hiroshi,Honsho, Yoshihito,Saito, Arihiro,Seki, Shu,Imahori, Hiroshi
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supporting information
p. 932 - 935
(2013/03/28)
-
- Sulfonyl-1,2,3-triazoles: Convenient synthones for heterocyclic compounds
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As easy as 1,2,3: Readily available and shelf-stable 1-sulfonyl-1,2,3- triazoles react with aldehydes and aldimines in the presence of RhII catalysts to produce 4-oxazolines and 1,2,5-trisubstituted imidazoles (see scheme). Copyright
- Zibinsky, Mikhail,Fokin, Valery V.
-
supporting information
p. 1507 - 1510
(2013/03/13)
-
- Copper-catalyzed cascade preparation of dihydropyrimidin-4-ones from N -(Prop-2-yn-1-yl)amides and azides
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Dihydropyrimidin-4-ones were efficiently synthesized from copper catalyzed reaction between N-(prop-2-yn-1-yl)amides and sulfonylazides under mild conditions in moderate to excellent yields (up to 96% yields). The cascade process involves the copper-catal
- Wang, Jinjin,Wang, Jing,Lu, Ping,Wang, Yanguang
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p. 8816 - 8820
(2013/09/24)
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- Catalytic asymmetric C-H insertions of rhodium(II) azavinyl carbenes
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A highly efficient enantioselective C-H insertion of azavinyl carbenes into unactivated alkanes has been developed. These transition metal carbenes are directly generated from readily available and stable 1-sulfonyl-1,2,3-triazoles in the presence of chiral Rh(II) carboxylates and are used for C-H functionalization of alkanes to access a variety of β-chiral sulfonamides.
- Chuprakov, Stepan,Malik, Jamal A.,Zibinsky, Mikhail,Fokin, Valery V.
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supporting information; experimental part
p. 10352 - 10355
(2011/08/05)
-
- Novel bisaryl substituted thiazoles and oxazoles as highly potent and selective peroxisome proliferator-activated receptor δ agonists
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The discovery, synthesis, and optimization of compound 1 from a high-throughput screening hit to highly potent and selective peroxisome proliferator-activated receptor δ (PPARδ) agonists are reported. The synthesis and structure-activity relationship in this series are described in detail. On the basis of a general schematic PPAR pharmacophore model, scaffold 1 was divided into headgroup, linker, and tailgroup and successively optimized for PPAR activation using in vitro PPAR transactivation assays. A (2-methylphenoxy)acetic acid headgroup, a flexible linker, and a five-membered heteroaromatic center ring with two hydrophobic aryl substituents were required for efficient and selective PPARδ activation. The fine-tuning of these aryl substituents led to an array of highly potent and selective compounds such as compound 38c, displaying an excellent pharmacokinetic profile in mouse. In an in vivo acute dosing model, selected members of this array were shown to induce the expression of pyruvate dehydrogenase kinase-4 (PDK4) and uncoupling protein-3 (UCP3), genes that are known to be involved in energy homeostasis and regulated by PPARδ in skeletal muscle.
- Epple, Robert,Cow, Christopher,Xie, Yongping,Azimioara, Mihai,Russo, Ross,Wang, Xing,Wityak, John,Karanewsky, Donald S.,Tuntland, Tove,Nguyê?-Tran, Van T. B.,Ngo, Cara Cuc,Huang, David,Saez, Enrique,Spalding, Tracy,Gerken, Andrea,Iskandar, Maya,Seidel, H. Martin,Tian, Shin-Shay
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experimental part
p. 77 - 105
(2010/04/30)
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- Concise synthesis of dimethyl (2-oxopropyl)phosphonate and homologation of aldehydes to alkynes in a tandem process
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The synthesis of dimethyl (diazomethyl)phosphonate, a useful reagent for the homologation of aldehydes to alkynes, is described as a one-pot process and comprises the generation of the azide transfer agent, diazotransfer to dimethyl (2-oxopropyl)phosphonate, and methanolysis, followed by a simple extraction protocol. Previously described syntheses for this bulk product are much more elaborate. The homologation of aldehydes to alkynes can also be extended to a single-step process by adding the aldehyde directly to the reaction mixture prior to isolation of the reagent. The homologation process using dimethyl (diazomethyl)phosphonate was shown to proceed also in nonprotic solvents with mild bases, emphasizing the importance of a facile access to the reagent. The oxidation of alcohols to the required aldehydes was performed by a TEMPO-mediated process using chloramine-T as electron acceptor. Copyright Taylor & Francis Group, LLC.
- Maehr, Hubert,Uskokovic, Milan R.,Schaffner, Carl P.
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experimental part
p. 299 - 310
(2009/04/10)
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- Divergent and expeditious access to fused skeletons inspired by indole alkaloids and transtaganolides
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We report the development of a divergent synthetic process entailing four-step access to the elaborate fused skeletons reminiscent of aspidophytines and transtaganolides. A variety of branched precursors were synthesized on the basis of Ugi condensations and installation of diazoimide and subjected to rhodium-catalyzed tandem reactions. Switching of cyclization modes was demonstrated by the choice of the amine building blocks installed at site C.
- Mizoguchi, Haruki,Oguri, Hiroki,Tsuge, Kiyoshi,Oikawa, Hideaki
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supporting information; experimental part
p. 3016 - 3019
(2009/12/05)
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- Cyanomethylamines and azidomethylamines: new general methods of the synthesis and transformations
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Simple and efficient methods have been developed to obtain cyanomethylamines and azidomethylamines using reactions of methoxymethylamines with TMSCN and TMSN3, respectively. In the case of dimethylformamide dimethylacetal, only one MeO group wa
- Nabiev, Orudzh G.,Nabizade, Zargalam O.,Kostyanovsky, Remir G.
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body text
p. 281 - 283
(2010/01/18)
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- Convenient one-pot synthesis of sulfonyl azides from sulfonic acids
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We have developed a one-pot process for preparing sulfonyl azides by treating sulfonic acids with trichloroacetonitrile, triphenylphosphine, and sodium azide at room temperature. A wide range of sulfonyl azides was synthesized in excellent yields under mild conditions. Georg Thieme Verlag Stuttgart.
- Kim, Joong-Gon,Doo, Ok Jang
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experimental part
p. 2885 - 2887
(2009/04/21)
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- COMPOUNDS AND COMPOSITIONS AS PPAR MODULATORS
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The invention provides compounds, pharmaceutical compositions comprising such compounds and methods of using such compounds to treat or prevent diseases or disorders associated with the activity of the Peroxisome Proliferator-Activated Receptor (PPAR) families.
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Page/Page column 20-21
(2010/11/27)
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- Hydrazines and azides via the metal-catalyzed hydrohydrazination and hydroazidation of olefins
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The discovery, study, and implementation of the Co- and Mn-catalyzed hydrohydrazination and hydroazidation reactions of olefins are reported. These reactions are equivalent to direct hydroaminations of C-C double bonds with protected hydrazines or hydrazoic acid but are based on a different concept in which the H and the N atoms come from two different reagents, a silane and an oxidizing nitrogen source (azodicarboxylate or sulfonyl azide). The hydrohydrazination reaction using di-tert-butyl azodicarboxylate is characterized by its ease of use, large functional group tolerance, and broad scope, including mono-, di-, tri-, and tetrasubstituted olefins. Key to the development of the hydroazidation reaction was the use of sulfonyl azides as nitrogen sources and the activating effect of tert-butyl hydroperoxide. The reaction was found to be efficient for the functionalization of mono-, di-, and trisubstituted olefins, and only a few functional groups are not tolerated. The alkyl azides obtained are versatile intermediates and can be transformed to the free amines or triazoles without isolation of the azides. Preliminary mechanistic investigations suggest a rate-limiting hydrocobaltation of the alkene, followed by an amination reaction. Radical intermediates cannot be ruled out and may be involved.
- Waser, Jerome,Gaspar, Boris,Nambu, Hisanori,Carreira, Erick M.
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p. 11693 - 11712
(2007/10/03)
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- A convenient method for the synthesis of dialkyl ethers by alkylation of alcohols using phosphinimidates in the presence of a catalytic amount of trimethylsilyl triflate
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An alkylation reaction of alcohols with alkyl N-(methylsulfonyl) diphenylphosphinimidates proceeded smoothly in the presence of a catalytic amount of trimethylsilyl triflate (Me3SiOTf) in DME at room temperature and the corresponding ethers were afforded in good to high yields. An alkyl N-(methylsulfonyl)diphenylphosphinimidate can be prepared easily from an alkyl diphenylphosphinite and methanesulfonyl azide, and is isolated without tedious operation. Moreover, it is easy to handle and can be stored for several months at room temperature because of its air- and moisture-resistant character. Also, one-pot tertiary alkylations of alcohols by using t-alkyl diphenylphosphinites and diphenoxyphosphoryl azide proceeded efficiently in the presence of a catalytic amount of Me3SiOTf in cyclohexane/CH 2Cl2 at 0°C or -10°C, and gave the corresponding tertiary alkyl ethers in good yields. By following these methods, various ethers having alkali-sensitive functional groups can be prepared easily.
- Aoki, Hidenori,Mukaiyama, Teruaki
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p. 1255 - 1264
(2007/10/03)
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- Towards a general scale of nucleophilicity?
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(Chemical Equation Presented) One for all? The nucleophilicity parameters N, which have been derived from the rate constants k of reactions of nucleophiles with carbocations, also hold for SN2-type reactions (see scheme). A general equation is suggested which includes established correlations (Swain-Scott, Ritchie) as special cases.
- Phan, Thanh Binh,Breugst, Martin,Mayr, Herbert
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p. 3869 - 3874
(2007/10/03)
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- A new approach to macrocyclization via alkene formation in catalytic diazo decomposition. Synthesis of patulolides A and B.
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[reaction: see text] Effective synthetic uses of bisdiazocarbonyl compounds for the selective construction of diverse macrocycles, including the synthesis of patulolides A and B, by catalytic "carbene dimer" formation are reported. Control of stereochemistry and efficient methods for product isomerization or kinetic isomer differentiation have been achieved.
- Doyle,Hu,Phillips,Wee
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p. 1777 - 1779
(2007/10/03)
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- Mechanisms of hydrolysis and related nucleophilic displacement reactions of alkanesulfonyl chlorides: pH dependence and the mechanism of hydration of sulfenes
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pH-rate profiles, primary kinetic isotope effects, deuterium substitution patterns, and pH-product ratios in the presence of added nucleophiles provide evidence for the following overlapping set of mechanisms for the hydrolysis of methanesulfonyl chloride (1) (in 0.1 M KCl at 25 °C): (a) pH ≤ 1-6.7, reaction with water by direct nucleophilic attack on the sulfonyl chloride; (b) pH ≥ 6.7-11.8, rate-determining attack by hydroxide anion to form sulfene (2), which is then trapped by water in a fast step; and (c) pH ≥ 11.8, sulfene formation and sulfene trapping by hydroxide anion; careful inspection showed no sign of sulfene formation in the reaction with water or of direct displacement by hydroxide anion. This pattern, with appropriate variations in the values of pHi (the pH at which two competing mechanisms have the same rate), is apparently general for simple alkanesulfonyl chlorides having at least one hydrogen on the carbon bearing the sulfonyl group. Azide and acetate anions react with 1 below pHi for 1 (6.7) by direct nucleophilic substitution at the sulfur, but above pHi by trapping of the sulfene. 2-Chlorophenoxide anion reacts with 1 below pH 6.7 by both (a) direct displacement to form the ester and (b) elimination to form the sulfene. Above pH 6.7, sulfene is formed from the sulfonyl chloride by reaction with either 2-chlorophenoxide or hydroxide ion; this is followed by trapping of the sulfene with 2-chlorophenoxide, water, or hydroxide. The possibility of the 2-chlorophenoxide anion acting as a general base promoting the reaction of water with either 1 and 2 was examined, but no sign of either process was detected.
- King,Lam,Skonieczny
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p. 1743 - 1749
(2007/10/02)
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- 1,3-Dipolar Cycloaddition of Electrophilic Azides to Cyclic Ketene N,X-Acetals. - Extrusion of Molecular Nitrogen and Ring Expansion of the Cycloadducts
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The electrophilic azides 2 react with cyclic ketene N,X-acetals of type 7, e.g. 13, 15, 18, 21, 23, 25, and with the alkylidenedihydroindoles 28 as well, to produce, besides molecular nitrogen, ring-expanded products of type 11 and 12, e.g. 14, 16, 19, 22
- Quast, Helmut,Ach, Manfred,Peters, Eva-Maria,Peters, Karl,Schnering, Hans Georg von
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p. 1259 - 1270
(2007/10/02)
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- 5-Imino-1,4,5,6-tetrahydro-1,2,3,4-tetrazines Formed from 5-Alkylidene-4,5-dihydro-1H-tetrazoles and Electrophilic Azides
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The electrophilic azides 1 react with the 5-alkylidenedihydrotetrazoles 8 already at low temperatures to produce high yields of the novel 5-iminotetrahydro-1,2,3,4-tetrazines 10 besides molecular nitrogen.The configurations of (Z)-10a, (E)-10c, (Z)-10d, a
- Quast, Helmut,Regnat, Dieter,Balthasar, Juergen,Banert, Klaus,Peters, Eva-Maria,et al.
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p. 409 - 416
(2007/10/02)
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- A convenient preparation of diazo carbonyl compounds under tri-phase phase-transfer catalysis conditions
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A simple and convenient one-pot preparation method for pure diazo carbonyl compounds under tri-phase phase-transfer catalysis conditions is described.
- Madan Kumar
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p. 2121 - 2127
(2007/10/02)
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- Electronic Structure and Gas-Phase Thermolysis of Substituted Tetrazolines Studied by Photoelectron Spectroscopy
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The electronic structures and the gas-phase thermolyses of terazolines 1-5 have been studied by photoelectron spectroscopy.For compounds 1-4 cyclorevision to imine and methyl azide is observed, whereas compound 5 is contracted to give the respective diaziridine.To assign the PE spectra, MNDO calculations were performed for compounds 1, 2, 4, and 5; some conformational properties of 5 have been studied by AM1 calculations.
- Rademacher, Paul,Carboni, Bertrand,Carrie, Robert,Heymanns, Peter,Poppek, Rainer
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p. 1213 - 1218
(2007/10/02)
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