- Electrochemical Difunctionalization of Styrenes via Chemoselective Oxo-Azidation or Oxo-Hydroxyphthalimidation
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Atom- and step-economic oxo-azidation and oxo-hydroxyphthalimidation of styrenes have been developed under mild electrolytic conditions, respectively. Various valuable alpha-azido or hydroxyphthalimide aromatic ketones were synthesized efficiently from readily available styrenes, azides, and N-hydroxyphthalimides. Mechanism studies show that two different pathways involved in these two transformations.
- Jiang, Haobin,Wang, Feng,Ye, Zenghui,Zhang, Fengzhi,Zhu, Rongjin
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supporting information
p. 8240 - 8245
(2021/11/17)
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- Concurrent Formation of N-H Imines and Carbonyl Compounds by Ruthenium-Catalyzed C-C Bond Cleavage of β-Hydroxy Azides
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A commercial cyclopentadienylrutenium dicarbonyl dimer ([CpRu(CO)2]2) efficiently catalyzes the formation of N-H imines and carbonyl compounds simultaneously from β-hydroxy azides via C-C bond cleavage under visible light. Density functional theory calculations for the cleavage reaction support the mechanism involving chelation of alkoxy azide species and liberation of nitrogen as the driving force. The synthetic utility of the reaction was demonstrated by a new amine synthesis promoted by chemoselective allylation of imine and synthesis of isoquinoline.
- Lee, Jeong Min,Bae, Dae Young,Park, Jin Yong,Jo, Hwi Yul,Lee, Eunsung,Rhee, Young Ho,Park, Jaiwook
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supporting information
p. 4608 - 4613
(2020/06/05)
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- Chemo- and Enantioselective Oxidative α-Azidation of Carbonyl Compounds
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We report high-performance I+/H2O2 catalysis for the oxidative or decarboxylative oxidative α-azidation of carbonyl compounds by using sodium azide under biphasic neutral phase-transfer conditions. To induce higher reactivity especially for the α-azidation of 1,3-dicarbonyl compounds, we designed a structurally compact isoindoline-derived quaternary ammonium iodide catalyst bearing electron-withdrawing groups. The nonproductive decomposition pathways of I+/H2O2 catalysis could be suppressed by the use of a catalytic amount of a radical-trapping agent. This oxidative coupling tolerates a variety of functional groups and could be readily applied to the late-stage α-azidation of structurally diverse complex molecules. Moreover, we achieved the enantioselective α-azidation of 1,3-dicarbonyl compounds as the first successful example of enantioselective intermolecular oxidative coupling with a chiral hypoiodite catalyst.
- Hattori, Yuhei,Ishihara, Kazuaki,Sahara, Naoto,Tsukahara, Mayuko,Uyanik, Muhammet
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supporting information
p. 17110 - 17117
(2020/08/10)
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- Visible-Light-Accelerated Copper(II)-Catalyzed Regio- and Chemoselective Oxo-Azidation of Vinyl Arenes
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The visible-light-accelerated oxo-azidation of vinyl arenes with trimethylsilylazide and molecular oxygen as stoichiometric oxidant was achieved. In contrast to photocatalysts based on iridium, ruthenium, or organic dyes, [Cu(dap)2]Cl or [Cu(dap)Cl2] were found to be unique for this transformation, which is attributed to their ability to interact with the substrates through ligand exchange and rebound mechanisms. CuII is proposed as the catalytically active species, which upon coordinating azide will undergo light-accelerated homolysis to form CuI and azide radicals. This activation principle (CuII-X→CuI+X.) opens up new avenues for copper-based photocatalysis.
- Hossain, Asik,Vidyasagar, Adiyala,Eichinger, Christian,Lankes, Christian,Phan, Jenny,Rehbein, Julia,Reiser, Oliver
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supporting information
p. 8288 - 8292
(2018/06/29)
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- Method for preparing alpha-azidoketone compounds based on photocatalysis
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The invention discloses a method for preparing alpha-azidoketone compounds based on photocatalysis. The method is based on a reaction formula shown in the description, wherein R is optionally-substituted aryl, heteroaryl or 1-12 carbon alkyl; R is o
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Paragraph 0178; 0179; 0180
(2018/10/11)
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- Iron-Catalyzed Acyl Migration of Tertiary α-Azidyl Ketones: Synthetic Approach toward Enamides and Isoquinolones
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This paper reports that tertiary α-azidyl phenyl ketones can be transformed into enamides by treatment with FeBr2 at elevated temperature in DMF. The reaction proceeds via 1,2-benzoyl migration from α-carbon to the nitrogen atom, accompanied by expulsion of a nitrogen molecule. This protocol is suitable for the synthesis of N-(cyclopent-1-en-1-yl)benzamides, N-(cyclohex-1-en-1-yl)benzamides, and N-benzoyl-α-methyl enamines and provides a convenient approach toward isoquinolones.
- Yang, Tonghao,Fan, Xing,Zhao, Xiaopeng,Yu, Wei
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p. 1875 - 1879
(2018/04/16)
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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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- α-N-Heteroarylation and α-Azidation of Ketones via Enolonium Species
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Enolonium species, resulting from the umpolung of ketone enolates by Koser's hypervalent iodine reagents activated by boron trifluoride, react with a variety of nitrogen heterocycles to form α-aminated ketones. The reactions are mild and complete in 4-5 h. Additionally, α-azidation of the enolonium species takes place using trimethylsilyl azide as a convenient source of azide nucleophile.
- More, Atul A.,Pathe, Gulab K.,Parida, Keshaba N.,Maksymenko, Shimon,Lipisa, Yuriy B.,Szpilman, Alex M.
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p. 2442 - 2447
(2018/02/23)
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- Visible-light-enabled oxyazidation of alkenes leading to α-azidoketones in air
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A new and facile visible-light-enabled method for the synthesis of α-azidoketones has been developed via oxyazidation of alkenes with TMSN3 in air at room temperature. A series of α-azidoketones could be easily and efficiently obtained in moder
- Wei, Wei,Cui, Huanhuan,Yue, Huilan,Yang, Daoshan
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supporting information
p. 3197 - 3202
(2018/07/29)
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- The synthesis of α-azidoesters and geminal triazides
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Three simple methods for the synthesis of geminal triazides are described: Starting from 1) 3-oxocarboxylic acids, 2) iodomethyl ketones, or 3) terminal olefins, a range of triazidomethyl ketones can be constructed under mild oxidative reaction conditions by the use of IBX-SO3K, a sulfonylated derivative of 2-iodoxybenzoic acid (IBX), and NaN3 as an azide source. This is the first report of representatives of this novel class of triazide compounds: Despite their high nitrogen content, the geminal triazides are easy to handle, even when preparative-scale syntheses are performed. (Caution: These procedures still require protective measures!) The triazides are now broadly available for further studies regarding their properties and reactivity. Furthermore, we show how the method can be used to provide α-azidoesters, which are potential building blocks for amino acids. Either/or: Geminal triazides are rapidly constructed with broad scope by the use of oxocarboxylic acids, iodomethyl ketones, or terminal olefins as starting substrates in oxidative azidations with a mild derivative of 2-iodoxybenzoic acid and sodium azide. Along with this little-studied class of organic azides, α-azidoesters were also synthesized.
- Klahn, Philipp,Erhardt, Hellmuth,Kotthaus, Andreas,Kirsch, Stefan F.
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supporting information
p. 7913 - 7917
(2014/08/05)
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- Azidation of β-keto esters and silyl enol ethers with a benziodoxole reagent
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The efficient azidation of β-keto esters and silyl enol ethers using a benziodoxole-derived azide transfer reagent is reported. The azidation of cyclic β-keto esters could be achieved in up to quantitative yields in the absence of any catalyst. In the case of less reactive linear β-keto esters and silyl enol ethers, complete conversion and good yields could be obtained by using a zinc catalyst.
- Vita, Maria Victoria,Waser, Jerome
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supporting information
p. 3246 - 3249
(2013/07/26)
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- Synthesis ofα-azido ketones and esters using recyclable hypervalent iodine reagent
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A simple and mild method for the preparation of αazido ketones and esters using hypervalent iodine reagent, 4,4'-bis-(dichloroiodo)-biphenyl, and sodium azide in 1,4-dioxane is discussed. Advantages of this system are easy workup, recyclable reagent, and
- Telvekar, Vikas N.,Patile, Hemlata V.
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experimental part
p. 131 - 135
(2011/02/27)
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- Iodobenzene-catalyzed synthesis of α-azidoketones and α-thiocyanatoketones from aryl ketones with MCPBA as a cooxidant
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Iodobenzene-catalyzed synthesis of α-azidoketones and α-thiocyanatoketones from aryl ketones with MCPBA as a cooxidant is described. The method is simple, rapid and practical, generating α-azidoketones and α-thiocyanatoketones from the aryl ketone without
- Chang, Ya-Li,Chung, Chi-Lin,Wu, Fang-Wen,Wang, Huey-Min,Hou, Rei-Sheu,Kang, Iou-Jiun,Chen, Ling-Ching
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p. 149 - 152
(2011/04/16)
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- Polymer-supported hypervalent iodine reagent mediated synthesis of α-azidoketones
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The reaction of aryl ketones with sodium azide using polymer-supported bis(trifluoroacetoxyiodo)-benzene (PSBTI) in the presence of trifluoroacetic acid (TFA) to prepare α-azidoketones in one-pot conditions is reported.
- Wang, Huey-Min,Hou, Rei-Sheu,Wu, Jian-Long,Chen, Ling-Ching
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p. 1333 - 1335
(2008/02/13)
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- [Hydroxy(tosyloxy)iodo]benzene mediated α-azidation of ketones
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Reaction of various ketones with [hydroxy(tosyloxy)iodo]benzene (HTIB) followed by treatment of the α-tosyloxy ketones thus generated in situ with NaN3 offers a one-pot procedure for the synthesis of α-azido ketones. The HTIB used in this conversion may also be generated in situ by using iodosobenzene in combination with p-toluene-sulphonic acid.
- Prakash, Om,Pannu, Kamaljeet,Prakash, Richa,Batra, Anita
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p. 523 - 527
(2007/10/03)
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- An effective synthesis of α-azido ketones from ketones
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One-pot transformation of ketones into α-azido ketones has been achieved by successive treatment with HNIB and NaN3 in acetonitrile.
- Lee,Kim,Shin
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p. 4271 - 4275
(2007/10/03)
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- A one step conversion of olefins into α-azidoketones using azidotrimethylsilane-chromium trioxide reagent system
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α-Azidoketones are conveniently obtained in good yields from the corresponding olefins upon reaction with azidotrimethylsilane-chromium trioxide reagent system.
- Venkat Ram Reddy,Kumareswaran,Vankar, Yashwant D.
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p. 6751 - 6754
(2007/10/02)
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- NEW APPLICATIONS OF IMINOPHOSPHORANES. THE PREPARATION OF β-KETO CARBODIIMIDES AND THEIR REARRANGEMENT TO 2-AMINO-1,3-OXAZOLES
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β-Keto carbodiimides (3) have been synthesized by reacting 2-azido ketones (1) with triphenylphosphine in the presence of isocyanates/isothiocyanates; the former compounds (3) are readily transformed into 2-amino-1,3-oxazoles (4).Key words: Synthesis; imi
- Froeyen, Paul
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- A New Versatile Synthesis of Oxazoles by Intramolecular Aza-Wittig Reaction
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A new synthesis of oxazoles by an intramolecular aza-Wittig reaction is described.Readily available α-azido ketones 2 were converted to (Z)-β-(acyloxy)vinyl azides 3 by selective enol acylation.These vinyl azides 3 reacted with triethyl phosphite to afford the corresponding oxazole derivatives 5 via the Staudinger reaction, followed by an intramolecular aza-Wittig reaction.In particular, this oxazole synthesis was useful for oxazoles having acid-labile substituents.
- Takeuchi, Hisato,Yanagida, Shun-ichi,Ozaki, Tooru,Hagiwara, Satoshi,Eguchi, Shoji
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p. 431 - 434
(2007/10/02)
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