- A General Catalytic Route to Enantioenriched Isoindolinones and Phthalides: Application in the Synthesis of (S)-PD 172938
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Chiral Br?nsted acid catalyzed enantioselective syntheses of isoindolinones and phthalides have been accomplished via tandem Mannich-lactamization and aldol-lactonization reactions, respectively. A variety of enantioenriched isoindolinones (up to 99% ee) and phthalides (up to 85% ee) containing α-diazoesters were afforded in excellent yields. Furthermore, a concise synthesis of (S)-PD 172938 has been demonstrated by using this protocol.
- Ray, Sumit K.,Sadhu, Milon M.,Biswas, Rayhan G.,Unhale, Rajshekhar A.,Singh, Vinod K.
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- One-step synthesis of cyclic polypyrazole and the self-assembly vesicles driven by hydrogen bond
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The synthesis of cyclic polymer is an important topic in polymer chemistry. Herein, we report a one-step method to prepare cyclic polypyrazoles. Monomers with two functional groups, diazo and alkyne, were synthesized and polymerized via 1,3-diploar cycloa
- Guo, Bogeng,Hou, Linxi,Lu, Zhen,Xiao, Longqiang,Zhao, Yulai
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- Fast Living Polymerization and Helix-Sense-Selective Polymerization of Diazoacetates Using Air-Stable Palladium(II) Catalysts
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In this work, air-stable palladium(II) catalysts bearing bidentate phosphine ligands were designed and prepared, which could initiate fast and living polymerizations of various diazoacetate monomers under mild conditions. The polymerization afforded the desired polymers in high yields with controlled molecular weights (Mns) and narrow molecular weight distributions (Mw/Mns). The Mns of the isolated polymers were linearly correlated to the initial feed ratios of monomer to catalyst, confirming the living/controlled manner of the polymerizations. The Mn also increased linearly with the monomer conversion, and all of the isolated polymers showed narrow Mw/Mns. The polymerization was relatively fast and could be accomplished within several minutes. Such fast living polymerization method can be applied to a wide range of diazoacetate monomers in various organic solvents at room temperature in air. Taking advantage of the living nature, we facilely prepared a series of block copolymers through chain extension reactions. The amphiphilic block copolymers synthesized by this method exhibited interesting self-assembly properties. Moreover, polymerization of achiral bulky diazoacetate by Pd(II) catalysts bearing a chiral bidentate phosphine ligand leads to the formation of polymers with high optical activity due to the formation of the predominantly one-handed helix of the main chain. The helix sense of the polymers was determined by the chirality of the Pd(II) catalysts.
- Chu, Jia-Hong,Xu, Xun-Hui,Kang, Shu-Ming,Liu, Na,Wu, Zong-Quan
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- Asymmetric transfer hydrogenation of heterocycle-containing acetophenone derivatives using N-functionalised [(benzene)Ru(II)(TsDPEN)] complexes
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The application of enantiomerically-pure ruthenium(II) catalysts containing N - functionalised TsDPEN ligand to the asymmetric transfer hydrogenation of 15 examples of α-heterocyclic acetophenone derivatives is reported. Products of up to 99% ee were formed.
- Barrios-Rivera, Jonathan,Xu, Yingjian,Clarkson, Guy J.,Wills, Martin
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supporting information
(2021/12/02)
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- ALCOHOL DERIVATIVES AS KV7 POTASSIUM CHANNEL OPENERS
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The present invention provides novel compounds which activate the Kv7 potassium channels. Separate aspects of the invention are directed to pharmaceutical compositions comprising said compounds and uses of the compounds to treat disorders responsive to the activation of Kv7 potassium channels.
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Paragraph 0210-0211
(2021/02/05)
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- Synthesis of 4-substituted-3-Hydroxyquinolin-2(1H)-ones with anticancer activity
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Herein we show that the 3-hydroxyquinolin-2(1H)-one (3HQ) core is a suitable platform to develop new compounds with anticancer activity against MCF-7 (IC50 up to 4.82 μM) and NCI–H460 (IC50 up to 1.8 μM) cancer cell lines. The ring-expansion reaction of isatins with diazo esters catalysed by di-rhodium (II) complexes proved to be a simple and effective strategy to synthesize 4-carboxylate-3HQs (yields up to 92%). 4-Carboxamide-3HQs were more efficiently prepared using NHS-diazoacetate in yields up to 88%. This innovative methodology enabled the construction of “peptidic-like” 3HQs, with several amino acid substituents. Among this series, the L-leucine derivative induced the cell death of MCF-7 (IC50 of 15.1 μM) and NCI–H460 (IC50 of 2.7 μM) cancer cell lines without causing any appreciable cytotoxicity against the non-cancer cell model (CHOK1).
- Paterna, Roberta,Padanha, Rita,Russo, Roberto,Frade, Raquel F.M.,Faustino, Hélio,Gois, Pedro M.P.
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supporting information
(2020/02/11)
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- A General Catalytic Route to Enantioenriched Isoindolinones and Phthalides: Application in the Synthesis of (S)-PD 172938
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Chiral Br?nsted acid catalyzed enantioselective syntheses of isoindolinones and phthalides have been accomplished via tandem Mannich-lactamization and aldol-lactonization reactions, respectively. A variety of enantioenriched isoindolinones (up to 99% ee) and phthalides (up to 85% ee) containing α-diazoesters were afforded in excellent yields. Furthermore, a concise synthesis of (S)-PD 172938 has been demonstrated by using this protocol.
- Ray, Sumit K.,Sadhu, Milon M.,Biswas, Rayhan G.,Unhale, Rajshekhar A.,Singh, Vinod K.
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supporting information
p. 417 - 422
(2019/01/23)
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- A chiral Br?nsted acid-catalyzed highly enantioselective Mannich-type reaction of α-diazo esters with in situ generated N -acyl ketimines
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A chiral phosphoric acid-catalyzed asymmetric Mannich-type reaction of α-diazo esters with in situ generated N-acyl ketimines, derived from 3-hydroxyisoindolinones has been demonstrated in this communication. A variety of isoindolinone-based α-amino diazo esters bearing a quaternary stereogenic center were afforded in high yields (up to 99%) with excellent enantioselectivities (up to 99% ee). Furthermore, the synthetic utility of the products has been depicted by the hydrogenation of the diazo moiety of adducts.
- Unhale, Rajshekhar A.,Sadhu, Milon M.,Ray, Sumit K.,Biswas, Rayhan G.,Singh, Vinod K.
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supporting information
p. 3516 - 3519
(2018/04/10)
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- Synthesis of C-Unsubstituted 1,2-Diazetidines and Their Ring-Opening Reactions via Selective N-N Bond Cleavage
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C-Unsubstituted 1,2-diazetidines, a rarely studied type of four-membered heterocyclic compounds, were synthesized through an operationally simple intermolecular vicinal disubstitution reaction. 1,2-Diazetidine derivatives bearing various N-arylsulfonyl groups were readily accessed and studied by experimental and computed Raman spectra. The ring-opening reaction of the diazetidine was explored and resulted in the identification of a selective N-N bond cleavage with thiols as nucleophiles, which stereoselectively produced a new class of N-sulfenylimine derivatives with C-aminomethyl groups.
- Chaminda Lakmal, Hetti Handi,Xu, Joanna Xiuzhu,Xu, Xue,Ahmed, Bassem,Fong, Christopher,Szalda, David J.,Ramig, Keith,Sygula, Andrzej,Webster, Charles Edwin,Zhang, Dongmao,Cui, Xin
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p. 9497 - 9503
(2018/06/22)
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- Synthesis of α-aminocarbonyl compounds via hetero dielsalder reaction
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A synthetic route to α-aminoketone derivatives via a hetero DielsAlder reaction is described. Diacylhydrazine was oxidized by tert-butyl hypochlorite in the presence of pyridine. After evaporation, the hetero DielsAlder reaction with diene was carried out without isolation of the azodicarbonyl compound. Quantitative hetero DielsAlder reaction was possible with 1 equivalent of diene when Hf(OTf)4 or AgOTf was used as the catalyst. The NN bond of the product was cleaved by SmI2-reduction in the presence of tert-BuOH in THF. Further, ozonolysis of the C=C double bond afforded the α-aminoketone derivative in excellent yield.
- Sakurai, Masayoshi,Kihara, Nobuhiro,Watanabe, Nobuhiro,Ikari, Yoshihiro,Takata, Toshikazu
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supporting information
p. 144 - 147
(2018/01/01)
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- Facile access to 2,2-disubstituted indolin-3-ones: Via a cascade Fischer indolization/Claisen rearrangement reaction
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An efficient approach for the synthesis of 2,2-disubstituted indolin-3-ones is described. From readily accessible aryl hydrazines and allyloxyketones, 2,2-disubstituted indolin-3-ones could be obtained in good to excellent yields under mild reaction condi
- Xia, Zilei,Hu, Jiadong,Gao, Yu-Qi,Yao, Qizheng,Xie, Weiqing
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supporting information
p. 7485 - 7488
(2017/07/12)
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- PREPARING METHOD OF HYDRIZIDE COMPOUNDS
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The present invention relates to a method for preparing hydrazide and, more specifically, to a method for preparing a hydrazide derivative compound by reacting a hydrazine-carbon dioxide coupled compound with an organic acid or sulfonic acid compound.COPYRIGHT KIPO 2015
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Paragraph 0128; 0218-0220
(2017/01/02)
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- Diazo ester insertion in NH bonds of amino acid derivatives and insulin catalyzed by water-soluble iron and ruthenium porphyrin complexes (FeTSPPCl) as application of carbenoid transfer in aqueous media
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The metal complex FeTSPPCl (5,10,15,20-tetrakis)-(4-sulfonato-phenyl)-porphyrin-iron(III) chloride is an active catalyst for carbenoid insertion in NH bonds of aminoacid derivatives in aqueous media. A variety of diazoacetates and methyl diazophosphonate
- Srour, Hassan F.,Maux, Paul Le,Chevance, Soizic,Carrié, Daniel,Yondre, Nicolas Le,Simonneaux, Gérard
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p. 194 - 203
(2015/07/27)
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- α-Bromodiazoacetamides - a new class of diazo compounds for catalyst-free, ambient temperature intramolecular C-H insertion reactions
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In this work, we introduce a new class of halodiazocarbonyl compounds, α-halodiazoacetamides, which through a metal-free, ambient-temperature thermolysis perform intramolecular C-H insertions to produce α-halo-β-lactams. When carried out with α-bromodiazoacetamides bearing cyclic side chains, the thermolysis reaction affords bicyclic α-halo-β-lactams, in some cases in excellent yields, depending on the ring size and substitution pattern of the cyclic amide side chains.
- Kaupang, Asmund,Bonge-Hansen, Tore
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supporting information
p. 1407 - 1413
(2013/08/23)
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- Insights into sulfinate formation from tosyl hydrazides
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Benzylation of 1,2-ditosylhydrazine in DMF under various basic conditions results in a benzyl sulfone via intermediary sulfinate formation, providing new insights and allowing practical conclusions to be drawn. The half-lives of 1,2-ditosylhydrazine and several monotosylated hydrazides with 1,1,3,3-tetramethylguanidine in DMSO have been determined by 1H NMR spectroscopy and are found to vary from a few minutes to several months. In the course of this work a benzylated, partly detosylated compound has been identified and a 1,1,3,3-tetramethyl guanidine-containing side-product characterized. A contradictory report is also commented on.
- Ragnarsson, Ulf,Grehn, Leif
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supporting information; experimental part
p. 1045 - 1047
(2012/03/27)
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- NOVEL MACROCYLES AND METHODS FOR THEIR PRODUCTION
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There are provided compounds of formula (I) or a pharmaceutically acceptable salt thereof: wherein the variables R1-R3 are as described in the description, said compounds being useful as anti-inflammatory agents with reduced systemic effects.
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Page/Page column 46
(2011/05/05)
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- NOVEL MACROCYCLES AND METHODS FOR THEIR PRODUCTION
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There are provided compounds of formula (I) or a pharmaceutically acceptable salt thereof: wherein the variables R1-R4 and X are as described in the description, said compounds being useful as anti-inflammatory agents with reduced sy
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Page/Page column 47; 48
(2011/05/05)
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- N,N′-ditosylhydrazine: A convenient reagent for facile synthesis of diazoacetates
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A novel entry to the synthesis of diazoacetates is disclosed. A variety of diazoacetates were synthesized from the corresponding bromoacetates by treatment with N,N′-ditosylhydrazine in moderate to high yields. Ease of operation with the stable crystalline reagent as well as a short reaction time offer a useful alternative to the conventional methods.
- Torna, Tatsuya,Shimokawa, Jun,Fukuyama, Tohru
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p. 3195 - 3197
(2008/02/10)
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- Silyl nitrogen compound: Part XV - Reactions of nonmetal halides with silylated tosylhydrazines
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Nonmetal halides EXn (E = C, Si, P, As, S; X = Br, Cl) and halogens (X = Br2,I2) react with bis(trimethylsilyl) tosylhydrazine, (Me3Si)2TsN2H to form tosylhydrazides, EXn-1(Me3Si)TsN2H, which on heating in vacuum, form a variety of azanes, hydrozones, diazenes and phophazanes. Ditosyltetrazene intermediate formed by dimerisation decomposes into ditosylhydrazine with liberation of nitrogen gas.
- Vasisht,Sharma, Anuradha
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p. 2113 - 2119
(2007/10/03)
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- Silyl-nitrogen compounds: Part XIII - Reactions of metal halides with silylated tosylhydrazines
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Bis(trimethylsilyl)tosylhydrazine (Me3Si)2TsN2H reacts with ECln (E=Al,Sn,Sb or Ti) to liberate Me3SiCl and in the process form tosylhydrazides, ECln·1(Me3Si)TsN2H. These compounds decompose on heating in vacuo to form a variety of azane derivatives with the loss of volatile products like Me3SiCl, HCl or SbCl3. Ditosyltetrazene intermediate decomposes into ditosylhydrazine whose structure is determined by X-ray diffraction.
- Vasisht,Venugopalan,Kataria, Jyoti,Sharma, Anuradha
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p. 2054 - 2059
(2007/10/03)
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- Nucleophilic substitution at a four-coordinate sulfur atom. IV. Reactivity of anionic nitrogen-containing nucleopiles
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The second-order rate constants for reactions of anions derived from azoles, arenesulfonamides, and arenesulfonohydrazides with aryl toluenesulfonates and methyl iodide in 5% aqueous ethanol (μ 1.0) at 25°C were compared with corresponding rate constants for aliphatic and heterocyclic amines. The kinetic behavior of neutral and anionic nitrogen-containing bases in reactions involving acyl (4-nitrophenyl acetate and 4-nitrophenyl heptanoate) and toluenesulfonyl group transfer suggests that deviation from the Bronsted dependence is due to unfavorable solvation effects for nucleophiles with pKa ≥ 11.0 rather than to change in the transition state structure. In reactions with a soft substrate, methyl iodide, solvation effects scarcely play the determining role, and the reduced reactivity of the anionic nucleophiles relative to neutral species is most likely to result from structural differences in the transition states corresponding to methyl group transfer to neutral and anionic nitrogen-containing compounds. The α-effect with arenesulfonohydrazides was revealed for the first time. 1996 MAEe Cyrillic signΚ Hayκa/Interperiodica Publishing.
- Savelova,Karpichev,Simanenko,Prokop'eva,Lobachev,Belousova
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p. 530 - 539
(2007/10/03)
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- Preparation and Reactions of N-Phenacyl-N-tosylhydroxylamines and -hydrazines
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O-Alkyl-N-phenacyl-N-tosylhydroxylamines 3 were prepared in two steps from O-alkylhydroxylamines 1.In the presence of a base the N-tosylhydroxylamines 3 undergo rearrangement and cleavage to N-tosylphenacylamine (5) and aldehydes 6.N-Alkyl-N'-phenacyl-N,N'-ditosylhydrazines 12 were obtained by stepwise treating of N,N'-ditosylhydrazine with alkyl halide and phenacyl bromide/potassium tert-butoxide/DMF
- Wessig, Pablo,Henning, Hans-Georg
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p. 983 - 986
(2007/10/02)
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- SYNTHESIS OF 10 - 13 MEMBERED TETRAAZACYCLOALKANES WITH A N,N'-BIS(2-AMINOETHYL)-HYDRAZINE UNIT IN THE RING
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A convenient method of synthesis of four new 10 -13 membered heteromacrocyclic systems with a N,N'-bis(2-aminoethyl)-hydrazine unit in the ring has been elaborated.This method consists in the cyclocondensation of the 1,2-diacylhydrazine alkali metal salts
- Goss, Ewa,Grudzinski, Stefan
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p. 305 - 312
(2007/10/02)
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