- A method for efficient synthesis of dinitrous compounds
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The present invention discloses a method for efficiently synthesizing a diazo compound, the method of organic matter with an active methylene as a raw material,NaN3 as an auxiliary reagent for diazo transfer,CH2Cl2 as a re
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Paragraph 0020-0024; 0025-0029
(2022/01/12)
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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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- Rhodium-Catalyzed Aerobic Decomposition of 1,3-Diaryl-2-diazo-1,3-diketones: Mechanistic Investigation and Application to the Synthesis of Benzils
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The conversion of 1,3-diaryl-2-diazo-1,3-diketones to 1,2-daryl-1,2-diketones (benzils) is reported based on a rhodium(II)-catalyzed aerobic decomposition process. The reaction occurs at ambient temperatures and can be catalyzed by a few dirhodium carboxylates (5 mol %) under a balloon pressure of oxygen. Moreover, an oxygen atom from the O2 reagent is shown to be incorporated into the product, and this is accompanied by the extrusion of a carbonyl unit from the starting materials. Mechanistically, it is proposed that the decomposition may proceed via the interaction of a ketene intermediate resulting from a Wolff rearrangement of the carbenoid, with a rhodium peroxide or peroxy radical species generated upon the activation of molecular oxygen. The proposed mechanism has been supported by the results from a set of controlled experiments. By using this newly developed strategy, a large array of benzil derivatives as well as 9,10-phenanthrenequinone were synthesized from the corresponding diazo substrates in varying yields. On the other hand, the method did not allow the generation of benzocyclobutene-1,2-dione from 2-diazo-1,3-indandione because of the difficulty of inducing the initial rearrangement.
- Zhu, Jia-Liang,Tsai, Yi-Ting
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p. 813 - 828
(2020/12/22)
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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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- Catalyst-Free Electrophilic Ring Expansion of N-Unprotected Aziridines with α-Oxoketenes to Efficient Access 2-Alkylidene-1,3-Oxazolidines
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2-(2-Oxoalkylidene)-1,3-oxazolidine derivatives were synthesized in good to excellent yields regiospecifically through the catalyst-free electrophilic ring expansion of N-unprotected aziridines and the ketene C=O double bond of α-oxoketenes, in situ generated from the microwave-assisted Wolff rearrangement of 2-diazo-1,3-diketones. The ring expansion predominantly underwent an SN1 process and the hydrogen bond decides the (E)-configuration of products. (Figure presented.).
- Chen, Xingpeng,Huang, Zhengshuo,Xu, Jiaxi
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supporting information
p. 3098 - 3108
(2021/05/10)
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- Iridium(III)-Catalyzed C(3)-H Alkylation of Isoquinolines via Metal Carbene Migratory Insertion
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An Ir(III)-catalyzed C(3)-H alkylation of N-acetyl-1,2-dihydroisoquinolines with diverse acceptor-acceptor diazo compounds has been achieved under a single catalytic system via metal carbene migratory insertion. Moreover, further synthetic transformations of the alkylated products such as aromatization, selective decarboxylation, and decarbonylation lead to the formation of several synthetically viable isoquinoline derivatives having immense potentials.
- Jha, Neha,Singh, Roushan Prakash,Saxena, Paridhi,Kapur, Manmohan
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supporting information
p. 8694 - 8698
(2021/11/24)
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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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supporting information
p. 6709 - 6713
(2021/09/08)
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- A 'sulfonyl-azide-free' (SAFE) aqueous-phase diazo transfer reaction for parallel and diversity-oriented synthesis
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Diazo transfer reactions are notoriously associated with the use of potentially explosive sulfonyl azides. The first 'sulfonyl-azide-free' (SAFE) protocol for producing diazo compounds from their active-methylene precursors via the Regitz diazo transfer reaction was developed and has displayed a remarkable substrate scope. It can be applied to generating arrays of diazo compounds for further evolution via combinatorial chemistry and a range of scaffold-generating transformations.
- Dar'In, Dmitry,Kantin, Grigory,Krasavin, Mikhail
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supporting information
p. 5239 - 5242
(2019/05/08)
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- Cycloaddition of α-Diazocarbonyl Compounds and N-Tosylaziridines: Synthesis of Polysubstituted 2 H-1,4-Oxazines through Synergetic Catalysis of AgOTf/Cu(OAc)2
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An impressive and new [3 + 3]-cycloaddition of α-diazocarbonyl compounds with N-tosylaziridines via synergetic catalysis of AgOTf and Cu(OAc)2 has been well described, which offers efficient access to highly substituted 2H-1,4-oxazine derivatives. A variety of α-diazocarbonyl compounds and N-tosylaziridines were compatible substrates with convenient operations under mild reaction conditions.
- Fang, Shangwen,Zhao, Yanwei,Li, Haiyan,Zheng, Yonggao,Lian, Pengcheng,Wan, Xiaobing
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supporting information
p. 2356 - 2359
(2019/03/29)
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- Rhodium(i)-catalyzed vinylation/[2 + 1] carbocyclization of 1,6-enynes with α-diazocarbonyl compounds
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A sequential Rh(i)-catalyzed vinylation/[2 + 1]carbocyclization between enynes and diazo compounds has been developed. This transformation features a wide range of enynes and acceptor/acceptor diazo compounds, providing easy access to versatile vinyl-substituted azabicyclo[3.1.0]hexanes having a broad tolerance to functional groups.
- Huang, Junmin,Hu, Xinwei,Chen, Fengjuan,Gui, Jiao,Zeng, Wei
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supporting information
p. 7042 - 7054
(2019/08/01)
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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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- 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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supporting information
p. 6756 - 6759
(2017/12/26)
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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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- Dichlorination of α-Diazo-β-dicarbonyls using (dichloroiodo)benzene
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Abstract α-Diazo-β-dicarbonyl compounds were chlorinated using (dichloro)iodobenzene and an activating catalyst. A broad range of reaction rates was observed, which paralleled the relative stability/nucleo-philicity of the diazo compounds. Acyclic diazocarbonyls reacted faster than cyclics, and β-diketones were much faster to react than β-keto esters or β-diesters. Lewis acid activation was used for the first time, allowing us to overcome instances of poor chemoselectivity. Though the yields ranged from low to good, this chlorination reaction has again proven a mild and effective halogenation strategy.
- Coffey, Keith E.,Murphy, Graham K.
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supporting information
p. 1003 - 1007
(2015/05/20)
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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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- 2-Azido-1,3-dimethylimidazolinium salts: Efficient diazo-transfer reagents for 1,3-dicarbonyl compounds
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We have developed the diazo-transfer of 2-azido-1,3-dimethylimidazolinium salts to 1,3-dicarbonyl compounds. 2-Azido-1,3-dimethylimidazolinium chloride (ADMC) was prepared by N-nitrosation of N-aminoguanidine or by the reaction of 2-chloro-1,3-dimethylimidazolinium chloride (DMC) and sodium azide. The corresponding phosphate, ADMP, was isolated as a crystal, and was found to be a stable and safe reagent. Both ADMC and ADMP reacted with 1,3-dicarbonyl compounds under mild conditions to give 2-diazo-1,3-dicarbonyl compounds in high yields, which are easily isolated because the by-products are highly soluble in water. Georg Thieme Verlag Stuttgart.
- Kitamura, Mitsuru,Tashiro, Norifumi,Miyagawa, Satoshi,Okauchi, Tatsuo
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experimental part
p. 1037 - 1044
(2011/06/20)
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- Synthesis of α-diazo carbonyl compounds with the shelf-stable diazo transfer reagent nonafluorobutanesulfonyl azide
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Nonafluorobutanesulfonyl azide is a shelf-stable, cost-effective and general diazo transfer reagent for the efficient synthesis of a-diazo carbonyl compounds in excellent yields and in very short reaction times, under mild conditions. The diazo products can be readily isolated in pure form after a simple aqueous extractive work-up that avoids chromatographic purification in most cases. Because of its high efficiency and wide substrate scope, shelf-stability, relatively low cost, and ease of product purification, nonafluorobutanesulfonyl azide offers an advantageous alternative to other commonly used diazo transfer reagents.
- Chiara, Jose Luis,Suarez, Jose Ramon
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supporting information; experimental part
p. 575 - 579
(2011/04/24)
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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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- 2-azido-1,3-dimethylimidazolinium chloride: An efficient diazo transfer reagent for 1,3-dicarbonyl compounds
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Diazo transfer from 2-azido-1,3-dimethylimidazolinium chloride to 1,3-dicarbonyl compounds has been developed. The -reaction proceeds under mild conditions to give 2-diazo-1,3-dicarbonyl compounds in high yields, which are easily isolated because the by-products are highly soluble in water. Georg Thieme Verlag Stuttgart.
- Kitamura, Mitsuru,Tashiro, Norifumi,Okauchi, Tatsuo
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scheme or table
p. 2943 - 2944
(2010/01/21)
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- Direct ionic liquid promoted organocatalyzed diazo-transfer reactions: diversity-oriented synthesis of diazo-compounds
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A practical and novel ionic liquid promoted organocatalytic selective diazo-transfer process for the synthesis of highly substituted diazo-compounds in high yields is reported. The ionic liquid can be reused without affecting the reaction rates or yields over five runs.
- Ramachary, Dhevalapally B.,Narayana, Vidadala V.,Ramakumar, Kinthada
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p. 2704 - 2709
(2008/09/19)
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- Efficient syntheses of some versatile 3,5-bifunctional pyrazole building blocks
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A series of convenient synthetic procedures are reported for pyrazole derivatives with carbonyl or ester groups in the 3- and 5-positions and variable substitution pattern at C4 and at the functional side arms. All compounds have been characterized by 1H and 13C NMR spectroscopy, elemental analyses, and mass spectrometry. In addition, the structures of several pyrazole derivatives have been determined by single crystal X-ray diffraction, which provides insight into the effect of functional side arms on the hydrogen-bonded supramolecular motifs of NH-pyrazoles. Georg Thieme Verlag Stuttgart.
- Sachse, Anna,Penkova, Larysa,Noel, Gilles,Dechert, Sebastian,Varzatskii, Oleg A.,Fritsky, Igor O.,Meyer, Franc
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p. 800 - 806
(2008/09/21)
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- Cycloaddition reaction of benzoheteroazepine: Synthesis of 4a,5,6,12-tetrahydro-1H-1,3-oxazino[3,2-d][1,5] benzothiazepin-1-ones and 1H,7H-1,3-oxazino[3,2-d][1,5] benzodiazepin-1-ones
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2,3-Dihydro-1,5-benzothiazepines and 2,3-dihydro-1H-1,5-benzodiazepines reacted with α -carbonylketenes, generated from 2-diazo-1,3-diphenyl-1,3-propanedione and 2-diazo-1-phenyl-1,3-butandione by heating, to give [2+4] cycloadducts 4a,5,6,12-tetrahydro-1H-1,3-oxazinop[3,2-d] [1,5]-benzothiazepin-1-ones and 4a,5,6,12-tetrahydro-1H,7H-1,3-oxazino [3,2-d][1,5]-benzodiazepin-1-ones. The cycloaddition reactions showed different regioselectivities when different 1,5-benzoheteroazepines reacted with asymmetric 2-diazo-1-phenyl-1,3-butandione. The conformations of cycloadducts and cycloadducts reaction mechanism were described.
- Xu, Jiaxi,Jin, Sheng,Xing, Qiyi
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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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- An improved synthesis of 2-diazo-1,3-diketones
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The sodium hydride/dibenzo-18-crown-6 ether system was found to be an effective base for the synthesis of 1,3-diketones by the Claisen condensation. The use of potassium fluoride (with or without crown ether) as the base in diazo-transfer reactions extends this reaction to the synthesis of hindered diazo diketones. In the case of isomeric 1,3-diketones, the stereoselectivity of the process considerably rises.
- Popic,Korneev,Nikolaev,Korobitsyna
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p. 195 - 198
(2007/10/02)
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- CYCLOADDITIONS OF DISUBSTITUTED DIAZO COMPOUNDS TO P-CHLORO(BISTRIMETHYLSILYL) METHYLENE PHOSPHINE.
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Disubstituted diazo compounds rapidly add to P-chloro (bistrimethylsilyl) methylene phosphine at low temperature. 1H, 31P and 13C NMR allow the characterization of the resulting cycloadducts and the establisment of the stereochemistry of the resulting cycloadducts which are potential precursors of ?3λ5 bis methylene phosphorane by nitrogen extrusion.
- Thoraval, J. Y.,Nagai, W.,Yeung Lam Ko, Y. Y. C.,Carrie, R.
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p. 3859 - 3868
(2007/10/02)
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- Azidotris(diethylamino)phosphonium bromide: A self-catalyzing diazo transfer reagent
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Acidic methylene compounds are conveniently converted to diazo compounds in high yields by azidotris(diethylamino)phosphonium bromide, 1, in diethyl ether using only a catalytic amount of base. The product diazo compounds are easily separated from the co-product hexaethylphosphorimidic triamide hydrobromide.
- McGuiness, Mark,Shechter, Harold
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p. 4987 - 4990
(2007/10/02)
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- POTASSIUM FLUORIDE ON ALUMINA: AN EASY PREPARATION OF DIAZOCARBONYL COMPOUNDS
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A convenient synthesis of diazocarbonyl compounds from tosyl azide and carbonyl compounds with Al2O3-KF as solid base is reported.
- Alloum, Abdelkrim Ben,Villemin, Didier
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p. 2567 - 2572
(2007/10/02)
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- Investigations on the Conformation of 2-Diazo-1,3-diketones
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Conformational analyses of 2-diazo-1,3-diketones (2a-f) with bulky substituents are performed by applying 1H- and 13C-NMR measurements in solution (and in solid state).
- Lauer, Wolfgang,Krause, Volker,Wegenroth, Horst,Meier, Herbert
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p. 465 - 470
(2007/10/02)
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- PREPARATION OF α-DIAZO-β-KETOSULFONES BY DIAZO-TRANSFER REACTION WITH AN IN SITU GENERATED AZIDINIUM SALT. A SAFE AND EFFICIENT PROCEDURE FOR THE DIAZO-TRANSFER REACTION IN NEUTRAL MEDIUM.
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An efficinet and mild procedure is described for the preparation of α-diazo-β-ketosulfones using an azidinium salt generated in situ from relatively inexpensive and safe chemicals.The method is equally applicable to other CH2-acidic compounds.
- Monteiro, H. J.
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p. 983 - 992
(2007/10/02)
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- β-Ketocarboxylic Esters with trans-Enolization
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Open-chained β-ketocarboxylic esters 10/11, existing predominantly in the E-configuration 2 of the enol form, can be generated by the introduction of mesityl groups.The energy gain by the intramolecular hydrogen bridge in the Z-configurations 1 is compens
- Meier, Herbert,Lauer, Wolfgang,Krause, Volker
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p. 3382 - 3393
(2007/10/02)
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