- SYNTHESIS OF SILYLDIAZOKETONES FROM LITHIUM PENTAMETHYLDISILANYLDIAZOMETHANE WITH ACID CHLORIDES
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Lithium pentamethyldisilanyldiazomethane, prepared from pentamethyldisilanyldiazomethane and lithium diisopropylamide, reacts with acid chlorides to give pentamethyldisilanyldiazoketones in good yields.
- Sekiguchi, Akira,Sato, Takashi,Ando, Wataru
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- Three-component synthesis of fluorinated pyrazoles from fluoroalkylamines, NaNO2 and electron-deficient alkynes
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Three-component reaction between RCF2CH2NH2·HCl, NaNO2 and electron-deficient alkynes significantly depends on substituent R . The reaction gives the fluorinated pyrazoles in high yields when R is a fluorine atom or a fluoroalkyl group. With other R unexpected products are formed.
- Mykhailiuk, Pavel K.
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- Photoinduced Multicomponent Synthesis of α-Silyloxy Acrylamides, an Unexplored Class of Silyl Enol Ethers
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The photoinduced, multicomponent reaction of α-diazoketones, silanols, and isocyanides affords α-silyloxy acrylamides, formally derived from α-keto amides. The presence of a secondary amido group makes classic preparative methods for silyl enol ethers unfeasible in this case, while the mild conditions required by this photochemical approach allow their synthesis in good yields; moreover, the general structure can be easily modified by varying each component of the multicomponent reaction. Fine-tuning of the reaction conditions (i.e., solvents, radiation, additives) can be exploited to obtain complete Z selectivity. The reactivity of this overlooked class of silyl enol ethers has been investigated, and features that could pave the way to new applications have been found.
- Ibba, Francesco,Capurro, Pietro,Garbarino, Silvia,Anselmo, Manuel,Moni, Lisa,Basso, Andrea
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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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- Exporting Metal-Carbene Chemistry to Live Mammalian Cells: Copper-Catalyzed Intracellular Synthesis of Quinoxalines Enabled by N?H Carbene Insertions
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Implementing catalytic organometallic transformations in living settings can offer unprecedented opportunities in chemical biology and medicine. Unfortunately, the number of biocompatible reactions so far discovered is very limited, and essentially restricted to uncaging processes. Here, we demonstrate the viability of performing metal carbene transfer reactions in live mammalian cells. In particular, we show that copper (II) catalysts can promote the intracellular annulation of alpha-keto diazocarbenes with ortho-amino arylamines, in a process that is initiated by an N-H carbene insertion. The potential of this transformation is underscored by the in cellulo synthesis of a product that alters mitochondrial functions, and by demonstrating cell selective biological responses using targeted copper catalysts. Considering the wide reactivity spectrum of metal carbenes, this work opens the door to significantly expanding the repertoire of life-compatible abiotic reactions.
- Gutiérrez, Sara,Mascare?as, José L.,Tomás-Gamasa, María
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supporting information
p. 22017 - 22025
(2021/08/30)
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- Oxoammonium Salt-Mediated Vicinal Oxyazidation of Alkenes with NaN3: Access to β-Aminooxy Azides
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An approach to the vicinal oxyazidation of alkenes has been achieved under mild and transition metal-free conditions. This method utilizes NaN3 as the azidation agent and 2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate (TEMPO
- Chen, Fei,Tang, Yu-Ting,Li, Xin-Ru,Duan, Yan-Yan,Chen, Chao-Xing,Zheng, Yang
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supporting information
p. 5079 - 5084
(2021/09/18)
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- Solvent-Directed Transition Metal-Free C-C Bond Cleavage by Azido-1,3,5-triazines and Their Stability-Reactivity Paradox
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We report a solvent-directed and regioselective carbon-carbon bond cleavage of aryl ketones by azido-1,3,5-triazines (ATs), which is typically completed within 10 min in DMSO at room temperature, without using transition metal catalysts. The cleavage is driven by the steric hindrance in the adducts of aryl ketones and ATs, which is substantiated by DFT calculation. Our recent results showed that ATs present high reactivity in solution and high stability in solid state. This "stability-reactivity paradox"has been explained in light of the molecular and crystal structures of ATs.
- Ma, Fulei,Xie, Xiaoyu,Li, Yuanheng,Yan, Ziqiang,Ma, Mingming
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p. 762 - 769
(2020/12/22)
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- Copper-Catalyzed 1,1-Alkylmonofluoroalkylation of Terminal Alkynes with Diazo Compounds and 2-Fluoro-1,3-dicarbonyl Compounds: Access toward (E)-β-Monofluoroalkyl-β,γ-unsaturated Esters or Ketones
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An efficient copper-catalyzed three-component 1,1-alkylmonofluoroalkylation of terminal alkynes, diazo compounds, and 2-fluoro-1,3-dicarbonyl compounds for the synthesis of (E)-β-monofluoroalkyl-β,γ-unsaturated esters or ketones has been developed. The methodology features a broad substrate scope, an inexpensive and easily available catalytic system, and excellent selectivity with good yields. The mechanism of the tandem Cu-catalyzed cross-coupling and nucleophilic addition of allenes has been investigated.
- Chen, Chen,Lv, Yunhe,Pu, Weiya,Wang, Shanshan,Zhu, Xueli
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p. 10043 - 10054
(2021/08/20)
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- B(C6F5)3-catalyzed O-H insertion reactions of diazoalkanes with phosphinic acids
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A highly efficient base-, metal-, and oxidant-free catalytic O-H insertion reaction of diazoalkanes and phosphinic acids in the presence of B(C6F5)3has been developed. This powerful methodology provides a green approach towards the synthesis of a broad spectrum of α-phosphoryloxy carbonyl compounds with good to excellent yields (up to 99% yield). The protocol features the advantages of operational simplicity, high atom economy, practicality, easy scalability and environmental friendliness.
- Jiang, Jun,Zhang, Xinzhi,Zhang, Yangyang,Zhao, Jincheng
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supporting information
p. 5772 - 5776
(2021/07/12)
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- Photoinduced Diverse Reactivity of Diazo Compounds with Nitrosoarenes
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A diverse reactivity of diazo compounds with nitrosoarene in an oxygen-transfer process and a formal [2 + 2] cycloaddition is reported. Nitosoarene has been exploited as a mild oxygen source to oxidize an in situ generated carbene intermediate under visible-light irradiation. UV-light-mediated in situ generated ketenes react with nitosoarenes to deliver oxazetidine derivatives. These operationally simple processes exemplify a transition-metal-free and catalyst-free protocol to give structurally diverse α-ketoesters or oxazetidines.
- Roy, Sourav,Kumar, Gourav,Chatterjee, Indranil
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p. 6709 - 6713
(2021/09/08)
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- Amino-modified Merrifield resins as recyclable catalysts for the safe and sustainable preparation of functionalized α-diazo carbonyl compounds
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Amino-functionalized polystyrene polymers derived from Merrifield resins were prepared and characterized. These basic materials were successfully employed as heterogeneous catalysts in the diazo transfer reaction to 1,3-dicarbonyl compounds, furnishing the corresponding diazo compounds in good to excellent yields and in relatively short reaction times. In addition, the work-up and purification protocols are simple and do not generate large amounts of waste, which are important features in sustainable catalysis and environmentally benign processes. The feasibility of the recovery and reuse of the amino-modified catalysts was also verified, since they can be employed up to five times without appreciable loss of catalytic activity. This straightforward procedure can be readily scaled up to gram scale, enabling the wide application of this method. The synthetic potential was demonstrated through the two-step preparation of 2-amino-N-dodecylacetamide (ANDA), a small molecule of commercial relevance.
- Fantinel, Mariane,Valiati, Nayara,Moro, Pedro A.M.,Sá, Marcus M.
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- Homologation of Electron-Rich Benzyl Bromide Derivatives via Diazo C-C Bond Insertion
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The ability to manipulate C-C bonds for selective chemical transformations is challenging and represents a growing area of research. Here, we report a formal insertion of diazo compounds into the "unactivated"C-C bond of benzyl bromide derivatives catalyzed by a simple Lewis acid. The homologation reaction proceeds via the intermediacy of a phenonium ion, and the products contain benzylic quaternary centers and an alkyl bromide amenable to further derivatization. Computational analysis provides critical insight into the reaction mechanism, in particular the key selectivity-determining step.
- Alegre-Requena, Juan V.,De Lescure, Louis,Modak, Atanu,Paton, Robert S.,Race, Nicholas J.,Rynders, Kathryn J.
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supporting information
(2021/12/27)
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- NovelN-transfer reagent for converting α-amino acid derivatives to α-diazo compounds
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A novel universalN-transfer reagent for direct and effective transformation of α-amino ketones, acetamides, and esters to the corresponding α-diazo products under mild basic conditions has been developed. This one-step synthetic approach not only allows for generation of α-substituted-α-diazo carbonyl compounds from α-amino acid derivatives but also permits preparation of α-diazo dipeptides fromN-terminal dipeptides (32 examples, up to 91%).
- Lu, Guan-Han,Huang, Tzu-Chia,Hsueh, Hsiao-Chin,Yang, Shin-Cherng,Cho, Ting-Wei,Chou, Ho-Hsuan
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supporting information
p. 4839 - 4842
(2021/05/25)
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- N-transfer reagent and method for preparing the same and its application
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Provided are a novel N-transfer reagent and a method for preparing the same and its application. The N-transfer reagent is represented by the following Formula (I): The various novel N-transfer reagents of the present invention can be quickly prepared by employing different nitrobenzene precursors. The N-transfer reagents can directly convert a variety of amino compounds into diazo compounds under mild conditions. Particularly, the N-transfer reagents can facilitate the synthesis of the diazo compounds. The application of synthesizing diazo compounds of the present invention can greatly decrease the difficulty in operation, increase the safety during experiments, reduce the cost of production and the environmental pollution, and enhance the industrial value of diazo compounds.
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Page/Page column 26-29; 59-60; 69-70
(2021/06/25)
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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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- Enantioselective dicarbofunctionalization of (: E)-alkenyloxindoles with pyridinium salts by chiral Lewis acid/photo relay catalysis
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A highly efficient enantioselective dicarbofunctionalization reaction of (E)-alkenyloxindoles with pyridinium salts was realized. The process includes the chiral N,N′-dioxide-Sc(iii) complex-catalyzed regio-, diastereo-, and enantioselective [3+2] cycloaddition reaction and the following photo-promoted aza-Norrish II type rearrangement. A series of 2-pyridyl substituted oxindole derivatives were obtained in good yields with moderate to good diastereo- and enantioselectivities. This journal is
- Zhang, Dong,Dong, Shunxi,He, Qianwen,Luo, Yao,Liu, Yun,Liu, Xiaohua,Feng, Xiaoming
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supporting information
p. 12757 - 12760
(2020/11/02)
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- Practical Application of the Aqueous 'Sulfonyl-Azide-Free' (SAFE) Diazo Transfer Protocol to Less α-C-H Acidic Ketones and Esters
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The earlier described 'sulfonyl-Azide-free' ('SAFE') protocol for diazo transfer to CH-Acidic 1,3-dicarbonyl compounds (and their similarly activated congeners) has been extended to the less reactive monocarbonyl substrates, which previously required a se
- Dar'In, Dmitry,Kantin, Grigory,Krasavin, Mikhail
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p. 4284 - 4290
(2019/11/14)
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- ELECTROPHILIC AZIDIZING AGENT OR DIAZOTIZING AGENT
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PROBLEM TO BE SOLVED: To provide a novel electrophilic azidizing agent that is safe without explosibility, capable of azidizing a nucleophilic compound in an electrophilic manner. SOLUTION: The present invention provides an azide imidazolium derivative re
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Paragraph 0084-0086
(2019/07/31)
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- Rhodium-mediated 18F-oxyfluorination of diazoketones using a fluorine-18-containing hypervalent iodine reagent
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Geminal 18F-oxyfluorination of diazoketones was performed in the presence of rhodium mediators. The reactions were performed using a hypervalent iodine-based [18F]fluoro-benziodoxole reagent. By this methodology various α-[18/s
- Cortés González, Miguel A.,Jiang, Xingguo,Nordeman, Patrik,Antoni, Gunnar,Szabó, Kálmán J.
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supporting information
p. 13358 - 13361
(2019/11/14)
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- Intermolecular acetoxyaminoalkylation of α-diazo amides with (diacetoxyiodo)benzene and amines
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Multicomponent reactions of diazo compounds have attracted much attention in recent years. Such transformations are generally conducted by applying transition metal catalysis and involve the corresponding metal carbenes as key intermediates. In this letter, a metal-free three-component intermolecular acetoxyaminoalkylation of α-diazo amides with tertiary aryl amines and (diacetoxyiodo)benzene is presented.
- D?ben, Nadine,Yan, Hong,Kischkewitz, Marvin,Mao, Jincheng,Studer, Armido
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supporting information
p. 7933 - 7936
(2019/01/04)
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- Metal-Free Insertion Reactions of Diazo Carbonyls to Azlactones
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Insertion reactions of diazo carbonyls to azlactones in basic conditions have been performed. The developed method allows the preparation of a wide range of oxazole derivatives in yields ranging from 74 to 98%. Different substituents on both azlactone rings and diazo carbonyls do not compromise the methodology, even those containing stereogenic centers. Isotopic labeling experiments revealed the mechanism may proceed through a rare diazo carbonyl activation by an ammonium salt derivative.
- De Mello, Amanda C.,Momo, Patrícia B.,Burtoloso, Antonio C. B.,Amarante, Giovanni W.
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p. 11399 - 11406
(2018/09/12)
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- Phosphoric Acid Catalyzed [4 + 1]-Cycloannulation Reaction of ortho-Quinone Methides and Diazoketones: Catalytic, Enantioselective Access toward cis-2,3-Dihydrobenzofurans
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A highly straightforward route to enantiomerically highly enriched cis-2,3-dihydrobenzofurans has been achieved via addition of α-diazocarbonyl compounds to in situ generated o-QMs catalyzed by a chiral Br?nsted acid. This catalytic strategy provides a direct access to 2,3-dihydrobenzofurans in high yields and with up to 91:9 dr and 99:1 er at ambient temperature. Moreover, a unique phenonium-type rearrangement accounts for product formation with an inverted 2,3-substitution pattern.
- Suneja, Arun,Schneider, Christoph
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supporting information
p. 7576 - 7580
(2019/01/03)
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- Site-Selective Conversion of Azido Groups at Carbonyl α-Positions to Diazo Groups in Diazido and Triazido Compounds
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This paper reports on the selective conversion of alkyl azido groups at the carbonyl α-position to diazo compounds. Through β-elimination of dinitrogen, followed by hydrazone formation/decomposition, α-azidocarbonyl moieties were transformed into α-diazo carbonyl groups in one step. As these reaction conditions do not involve aryl or general alkyl azides, site-selective conversions of di- and triazides were achieved. Through this method, the successive site-selective conjugation of the triazido molecule with three different components is demonstrated.
- Yokoi, Taiki,Tanimoto, Hiroki,Ueda, Tomomi,Morimoto, Tsumoru,Kakiuchi, Kiyomi
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p. 12103 - 12121
(2018/10/09)
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- A Sequential Route to Cyclopentenes from 1,6-Enynes and Diazo Ketones through Gold and Rhodium Catalysis
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This work reports the construction of cyclopentene cores from 1,6-enynes and aryl diazo ketones through two new reaction sequences involving initial gold-catalyzed cyclization of 1,6-enynes with diazo species, followed by rhodium-catalyzed skeletal rearrangement of the resulting 3-cyclopropyl-2-en-1-ones. In most instances the rhodium-catalyzed reactions afforded cyclopentene derivatives whereas several n-alkyl- or ortho-substituted phenyl ketones delivered seven-membered oxacycles. A plausible mechanism provides rationales for these two distinct products. (Figure presented.).
- Kale, Balaji S.,Lee, Hsin-Fu,Liu, Rai-Shung
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p. 402 - 409
(2017/02/10)
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- One-pot synthesis of trans-β-lactams from ferrocenylketene generated by thermal Wolff rearrangement
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A series of β-lactams containing the ferrocene moiety were synthesized through the Staudinger reaction between ferrocenylketene generated by the thermal Wolff rearrangement of the corresponding diazo ketone and various imines. The stereochemical outcome h
- Liu, Mingshun,Wang, Jian’an,Yuan, Xiaoxi,Jiang, Rong,Fu, Nanyan
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supporting information
p. 2369 - 2377
(2017/12/12)
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- Tandem Synthesis of α-Diazoketones from 1,3-Diketones
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A highly efficient synthesis of α-diazoketone was achieved by simply stirring the mixture of 1,3-diketone, TsN3, and MeNH2 in EtOH. It was a tandem reaction including a novel primary amine-catalyzed Regitz diazo transfer of 1,3-diket
- Zhang, Jianlan,Chen, Wenwen,Huang, Dayun,Zeng, Xiaobao,Wang, Xinyan,Hu, Yuefei
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p. 9171 - 9174
(2017/09/11)
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- Direct Carboxylation of the Diazo Group ipso-C(sp2)-H bond with Carbon Dioxide: Access to Unsymmetrical Diazomalonates and Derivatives
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The direct carboxylation of the ipso-C(sp2)-H bond of a diazo compound with carbon dioxide under mild reaction conditions is described. This method is transition-metal-free, uses a weak base, and proceeds at ambient temperature under atmospheric pressure in carbon dioxide. The carboxylation exhibits high reactivity and is amenable to subsequent diversification. A series of unsymmetrical 1,3-diester/keto/amide diazo compounds are obtained with moderate to excellent yields (up to 99%) with good functional group compatibility.
- Liu, Qianyi,Li, Man,Xiong, Rui,Mo, Fanyang
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p. 6756 - 6759
(2017/12/26)
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- Copper Triflate Mediated α-Monohalogenation of α-Diazo β-Ketosulfones with Ammonium Halides
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Copper triflate mediated α-monohalogenation of α-diazo β-ketosulfones with ammonium halides provides the corresponding α-halo β-ketosulfones. Different metal triflates are investigated for this facile and efficient transformation. A plausible mechanism is proposed.
- Chan, Chieh-Kai,Wang, Heui-Sin,Hsu, Ru-Ting,Chang, Meng-Yang
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p. 2045 - 2056
(2017/04/26)
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- Fluoride-Mediated Dephosphonylation of α-Diazo-β-carbonyl Phosphonates
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The possibility of fluoride-mediated selective dephosphonylation of α-diazo-β-carbonyl phosphonates such as the Ohira-Bestmann reagent has been proposed and executed. The resulting α-diazocarbonyl intermediates undergo a (3 + 2)-cycloaddition at room temperature with conjugated olefins and benzynes. Interestingly, under the current conditions, the resulting cycloaddition products underwent either N-acylation (with excess α-diazo-β-carbonyl phosphonates) or Michael addition (with conjugated olefins).
- Phatake, Ravindra S.,Mullapudi, Venkannababu,Wakchaure, Vivek C.,Ramana, Chepuri V.
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supporting information
p. 372 - 375
(2017/04/21)
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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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- An efficient PEG-400 mediated catalyst free green synthesis of 2-amino-thiazoles from α-diazoketones and thiourea
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A simple and efficient method has been developed for the synthesis of 2-aminothiazoles from α-diazoketones using PEG-400 solvent system. This novel synthetic approach involves the reaction between thiourea and α-diazoketones in PEG-400 at 100 °C to yield the corresponding 2-aminothiazoles in good yields. The method is simple, rapid and generates thiazole derivatives in excellent yields without the use of any catalysts. This green protocol can be utilized for fast synthesis of various 2-aminothiazoles in good yields. [Figure not available: see fulltext.]
- Babu, B Hari,Vijay,Murali Krishna, K Bala,Sharmila,Ramana, M Baby
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p. 1475 - 1478
(2016/09/19)
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- Iron-Catalyzed Annulation of 1,2-Diamines and Diazodicarbonyls for Diverse and Polyfunctionalized Quinoxalines, Pyrazines, and Benzoquinoxalines in Water
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A novel and facile iron-catalyzed tandem annulation of o-phenylenediamines and diazocarbonyls in water for the construction of polyfunctionalized quinoxalines has been developed. The key strategy includes the one-pot domino N?H insertion, cyclization, and
- Pandit, Rameshwar Prasad,Kim, Sung Hong,Lee, Yong Rok
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supporting information
p. 3586 - 3599
(2016/11/25)
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- Synthesis of Sulfonyldiazomethanes and Acetyldiazomethanes via an Alumina-Mediated Decarboxylation Strategy
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Diazo compounds are widely adopted in organic synthesis due to their carbine characteristics. One of the most interesting diazo compounds is diazolsulfonyl. Here, in the current study, we found that diazolsufonyl compounds could be prepared with moderate
- Yan, Yiyong,Ma, Gaoyuan,Wei, Wei,Zhao, Jing
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p. 239 - 242
(2016/02/18)
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- One-pot synthesis of polyfunctional pyrazoles: An easy access to α-diazoketones from arylglyoxal monohydrates and tosylhydrazine
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A new and efficient method for the generation of α-diazoketones has been developed from arylglyoxal monohydrates and tosylhydrazine at room temperature. 1,3-Dipolar cycloaddition reactions were used to constructing polyfunctional pyrazole derivatives by the reaction of generated α-diazoketones in situ with electron-deficient alkenes, quinones and coumarins in one pot. The one-dimensional molecular packing of 1H-benzo[f]indazole-4,9-dione derivatives along the c direction demonstrated a helical chain formation via N-H?O hydrogen-bonding.
- Shu, Wen-Ming,Ma, Jun-Rui,Zheng, Kai-Lu,Sun, Hui-Ying,Wang, Mei,Yang, Yan,Wu, An-Xin
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p. 9321 - 9329
(2015/03/05)
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- COMPOUNDS AND METHODS for the inhibition of HDAC
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Disclosed are compounds having the formula: wherein X1, X2, X3, R1, R2, R3, R4, Y, A, Z, L and n are as defined herein, and methods of making and using the same.
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Paragraph 0709-0710
(2015/11/24)
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- Enaminones via ruthenium-catalyzed coupling of thioamides and α-diazocarbonyl compounds
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Enaminones can be prepared via the Rh2(OAc)4- catalyzed coupling of α-diazocarbonyl compounds with thioamides. However, rhodium is the most expensive and least abundant among the dominant precious metals used for catalysis. Furthermore, a very limited substrate scope is known for the intermolecular rhodium catalyzed coupling reaction. Therefore, there is a need to find a more economical catalyst substitute with a broad substrate scope. In this paper, we describe the use of Ru(II) catalysts for the synthesis of enaminones. The reaction can be performed efficiently with the Grubbs first-generation catalyst or [(Ph)3P]3RuCl2 in a sealed tube. Both catalysts are much less expensive than Rh 2(OAc)4. Secondary and tertiary thioamides, when reacted with α-diazodiesters, α-diazoketoesters, α-diazodiketones, and α-diazomonoketones give enaminones. Primary thioamides give thiazole derivatives when reacted with α-diazomonoketones. However, with other diazo compounds, primary thioamides also give enaminones. All enaminones are obtained in good yields and with good diastereoselectivity. Accordingly, the method described in this paper is an efficient and economical alternative to the Rh2(OAc)4-catalyzed coupling process.
- Koduri, Naga D.,Wang, Zhiguo,Cannell, Garrett,Cooley, Kate,Lemma, Tsebaot Mesfin,Miao, Kun,Nguyen, Michael,Frohock, Bram,Castaneda, Maria,Scott, Halee,Albinescu, Dragos,Hussaini, Syed R.
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p. 7405 - 7414
(2014/09/17)
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- Templated carbene metathesis reactions from the modular assembly of enol-diazo compounds and propargyl acetates
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A Lewis acid mediated coupling reaction of enol-diazo nucleophiles and propargyl acetates has provided rapid and diverse access to complex alkynyl-tethered diazocarbonyl compounds. The ability of the coupling reaction to vary critical functionality flanking the diazo group was explored as a way to direct the outcome of a series of metal-catalyzed carbene metathesis cascade reactions. These cascade reactions provided diverse, biologically interesting carbocyclic and heterocyclic compounds in only a few steps from readily available materials. A general coupling strategy for the formation of alkynyl-substituted diazocarbonyl templates for catalytic cascade reactions is described. With the synthetic flexibility imparted to the coupling process and the facile cyclization of the first-formed metal carbene to secondary vinyl carbene templates, selective ylide, C-H insertion, and atom-transfer processes provide directed functionalization in cyclic compounds.
- Qian, Yu,Shanahan, Charles S.,Doyle, Michael P.
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p. 6032 - 6037
(2013/09/24)
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- TAK1 KINASE INHIBITORS, COMPOSITIONS, AND USED RELATED THERETO
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The disclosure relates to TAK1 inhibitors, compositions, and uses related thereto. In certain embodiments, the disclosure relates to compounds of formula (I), pharmaceutical compositions having a compound of formula (I), and methods of treating or prevent
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Page/Page column 53
(2013/03/26)
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- Amination of phenylketene revisit. Substituent effect on reactivity
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The asymmetric stretching frequencies of the ketene group of the m,p-substituted phenylketenes were found to be correlated with σ The substituent effects for the second-order rate constants of phenylketenes with various amines were not correlated linearly
- Badal, Md. Mizanur Rahman,Zhang, Min,Kobayashi, Shinjiro,Mishima, Masaaki
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p. 856 - 863
(2013/08/15)
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- Stability of diazocarbonyl compounds under the conditions of gas chromatography and chromatography-mass spectrometry analysis
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The gas chromatographic analysis of alkyldiazoacetates N 2CHCO2R (R = CH3 - C4H9), α-aliphatic diazoketones RCOCHN2 (R = C3H 7, C5H11, and C9H19), and aryl-substituted diazoketones Ph (CH2)nCOCHN2 (n = 0-2) is shown to be possible when their retention temperatures are below the boiling points of compounds of this series at atmospheric pressure without decomposition (about 140°C). At higher temperatures occurs partial or complete decomposition of α-diazoketones in chromatographic columns to form ketenes. Among the impurities in the reaction mixtures at the diazotization of corresponding alkyl glycinates were identified for the first time the nitrate esters of glycolic acid O2NOCH2CO2R, as well as the dimeric products. All diazocarbonyl compounds and the impurities were characterized by mass spectra. For the first time their gas chromatographic retention indices were determined. Pleiades Publishing, Ltd., 2012.
- Kornilova,Ukolov,Kostikov,Zenkevich
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p. 1675 - 1685
(2013/02/23)
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- Synthesis of ionic liquid-supported sulfonyl azide and its application in diazotransfer reaction
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The paper describes synthesis of a novel ionic liquid-supported sulfonyl azide and its applications as diazotransfer reagent of active methylene compounds as well as deformylative diazo transfer reagent. The diazo compounds were isolated in excellent yields (82-94%) and high purity. The method offers better separation of product and reagent. This method is experimentally simple and mild, and requires very short reaction time.
- Muthyala, Manoj Kumar,Choudhary, Sunita,Kumar, Anil
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p. 8787 - 8791
(2012/11/07)
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- Rhodium(II)-catalyzed cross-coupling of diazo compounds
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Nothing left to chance: A convenient protocol for selective cross-coupling of diazo compounds for the convergent synthesis of alkenes was developed (see scheme; EDG=aryl, heteroaryl, vinyl; R=O-alkyl, aryl). The selectivity control elements were identifie
- Hansen, Joorn H.,Parr, Brendan T.,Pelphrey, Philip,Jin, Quihui,Autschbach, Jochen,Davies, Huw M. L.
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supporting information; experimental part
p. 2544 - 2548
(2011/04/27)
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- Stereoselective control in the Staudinger reactions involving monosubstituted ketenes with electron acceptor substituents: Experimental investigation and theoretical rationalization
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The stereoselectivity of the Staudinger reactions involving monosubstituted ketenes with electron acceptor substituents was investigated experimentally by determination of the product stereochemistry and theoretically via DFT calculations. The results indicate that imines preferentially attack the less sterically hindered exo-side of the ketenes to generate zwitterionic intermediates. Subsequently, for cyclic imines, the intermediates undergo a conrotatory ring closure directly to produce β-lactams, while for linear imines, the imine moiety of the intermediates isomerizes to more stable intermediates, which further undergo a conrotatory ring closure to afford trans-β-lactams. The steric hindrance and the isomerization, rather than the torquoelectronic effect, play crucial roles in controlling the stereoselectivity in the practical Staudinger reactions involving monosubstituted ketenes with electron acceptor substituents, although the unaccessible borylketene with a powerful electron acceptor group controls the stereoselectivity torquoelectronically, in theory.
- Qi, Hengzhen,Li, Xinyao,Xu, Jiaxi
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supporting information; experimental part
p. 2702 - 2714
(2011/05/19)
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- Expeditious synthesis of 2,3,6-trisubstituted 2 H -1,3-oxazin-4(3 H)-ones via the tertiary amine-induced reaction of 2-diazo-3-oxoalkanals and imines under mild conditions
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A series of 2,3,6-trisubstituted 2H-1,3-oxazin-4(3H)-one derivatives were conveniently synthesized in satisfactory to good yields by the reaction of imines with 2-diazo-3-oxoalkanals in the presence of a catalytic amount of a tertiary amine during several seconds under mild condition. Different bases and -diazo - dicarbonyl compounds were also evaluated and a reaction mechanism is proposed. Compared with the corresponding thermal- and photo-induced- reactions, the current method is a metal-free, mild, highly regioselective, and more efficient approach for the synthesis of 2H-1,3-oxazin-4(3H)-one derivatives. Georg Thieme Verlag Stuttgart - New York.
- Qi, Hengzhen,Zhang, Jiantao,Xu, Jiaxi
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supporting information; experimental part
p. 887 - 894
(2011/05/05)
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- Continuous in situ generation, separation, and reaction of diazomethane in a dual-channel microreactor
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A fierce dog: A method for the continuous in-situ on-demand generation, separation, and reaction of diazomethane in a dual-channel microreactor has been developed (see picture; Diazald=N-methyl-N-nitroso-p-toluenesulfonamide). The microchemical system allows a variety of diazomethane reactions to be performed without the most common problems of preparation, handling, transfer, and decomposition.
- Maurya, Ram Awatar,Park, Chan Pil,Lee, Jang Han,Kim, Dong-Pyo
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experimental part
p. 5952 - 5955
(2011/08/02)
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- Safe and reliable synthesis of diazoketones and quinoxalines in a continuous flow reactor
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A flow method for the synthesis of aliphatic and aromatic diazoketones from acyl chloride precursors has been developed and used to prepare quinoxalines in a multistep sequence without isolation of the potentially explosive diazoketone. The protocol showcases an efficient in-line purification using supported scavengers with time-saving and safety benefits and in particular a reduction in the operator's exposure to carcinogenic phenylenediamines.
- Martin, Laetitia J.,Marzinzik, Andreas L.,Ley, Steven V.,Baxendale, Ian R.
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supporting information; experimental part
p. 320 - 323
(2011/03/23)
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- Improved arndt-eistert synthesis of α-diazoketones requiring minimal diazomethane in the presence of calcium oxide as acid scavenger
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A practical methodology to obtain α-diazoketones through an improved Arndt-Eistert synthesis is described. The method allows the efficient transformation of acid halides using a stoichiometric amount of diazomethane in the presence of calcium oxide, witho
- Pace, Vittorio,Verniest, Guido,Sinisterra, Josep-Vicent,Alcantara, Andres R.,De Kimpe, Norbert
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supporting information; experimental part
p. 5760 - 5763
(2010/10/03)
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- Trimethylsilyldiazomethane as a versatile stitching agent for the introduction of aziridines into functionalized organic molecules
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A highly enantioselective route for the introduction of aziridines into functionalized organic molecules was developed via a tandem acylation and aziridination of TMSCHN2.
- Ren, Hong,Wulff, William D.
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p. 4908 - 4911
(2011/02/21)
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- PREPARATION OF DIAZO AND DIAZONIUM COMPOUNDS
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A method for making diazo-compounds, diazonium salts thereof and other protected forms of these compounds. Diaz-compounds are prepared by reaction of a tertiary phosphine reagent carrying a reactive carbonyl group with an azide. The reaction can also generate an acyl triazene which can be converted thermally or by addition of base to form the diazo-compound or the acyl triazene can be isolated. The method is particularly useful for conversion of azides carrying one or more electron withdrawing groups to diazo-compounds. The method can be carried out in aqueous medium under mild conditions and is particularly useful for conversion of azido sugars to diazo-compound and diazonium salts thereof under physiological conditions. Tertiary phosphine reagents, particularly those that are water-soluble, and precursors for preparation of the reagents are provided.
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Page/Page column 32
(2010/06/13)
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- A cascade approach to pyridines from 2-Azido-2,4-dienoates and α-diazocarbonyl compounds
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A one-pot synthesis of substituted pyridines via a cascade reaction of 2-azido-2,4-dienoates with α-diazocarbonyl compounds and triphenylphosphine is reported. The process involves a Staudinger-Meyer reaction, a Wolff rearrangement, an aza-Wittig reaction, and an electrocyclic ring- closure. The procedure is general and efficient. The substrates are readily available.
- Chen, Zheng-Bo,Hong, Deng,Wang, Yan-Guang
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supporting information; experimental part
p. 903 - 905
(2009/06/20)
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