- A new method for the synthesis of N-protected β-amino-α-keto esters from fluoroalkanesulfonylazides and α-keto esters
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In the presence of a secondary amine, treatment of α-keto esters with fluoroalkanesulfonyl azides at room temperature afforded N-sulfonyl protected β-amino-α-keto esters in good to excellent yields. This reaction provided a novel, direct and convenient access to N-sulfonyl protected β-amino-α-keto esters from α-keto esters and fluoroalkanesulfonyl azides under mild conditions. However, the reaction of fluoroalkanesulfonyl azides with β-ketoester enamines afforded two products: N-fluoroalkanesulfonyl amidines and diazoacetate. The reaction mechanism is discussed.
- Zhu, Shizheng,Jin, Guifang,Xu, Yong
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- Solvent-Directed Click Reaction between Active Methylene Compounds and Azido-1,3,5-triazines
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A novel solvent-directed click reaction between active methylene compounds and azido-1,3,5-triazines has been developed. In aqueous solution, the regiospecific trisubstituted 1,2,3-triazole products are quickly synthesized in high yields under mild conditions and easy to separate without column chromatography. This click reaction is controlled by the protonation of a nitrogen anion intermediate, and the postulated mechanism is substantiated by DFT calculations.
- Yan, Ziqiang,Li, Yuanheng,Ma, Mingming
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- Development of a povarov reaction/carbene generation sequence for alkenyldiazocarbonyl compounds
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Rings aplenty: A HOTf-catalyzed (Tf=trifluoromethanesulfonyl) Povarov reaction of alkenyldiazo species has been developed and delivers diazo-containing cycloadducts stereoselectively (see scheme). The resulting cycloadducts provide access to six- and seven-membered azacycles through the generation of metal carbenes as well as the functionalization of diazo group. Copyright
- Jadhav, Appaso Mahadev,Pagar, Vinayak Vishnu,Liu, Rai-Shung
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- Efficient solid/liquid phase-transfer catalytic diazo transfer synthesis
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A simple and efficient solid/liquid phase-transfer catalytic diazo transfer reaction for the synthesis of diazocarbonyl, diazophosphonyl, and diazophosphinyl compounds is reported. Copyright
- Jaszay, Zsuzsa M.,Pham, Truong Son,Goenczi, Katalin,Petnehazy, Imre,Toke, Laszlo
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- Rh(III)-catalyzed chelation-assisted intermolecular carbenoid functionalization of α-imino Csp3-H bonds
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A Rh(iii)-catalyzed cross-coupling/cyclization cascade of α-imino Csp3-H bonds with donor/acceptor α-acyl diazocarbonyl compounds has been developed. This novel transformation involves ligand-directed Csp3-H bond functionalization with carbenoids under the pyridine-chelation assistance, and offered an efficient access to synthetically versatile polysubstituted N-(2-pyridyl)pyrroles with a broad range of functional group tolerance.
- Chen, Xun,Xie, Ying,Xiao, Xinsheng,Li, Guoqiang,Deng, Yuanfu,Jiang, Huanfeng,Zeng, Wei
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- A dual-protein cascade reaction for the regioselective synthesis of quinoxalines
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In this work, an efficient dual-protein (lipase and hemoglobin) system was successfully constructed for the regioselective synthesis of quinoxalines in water. A set of quinoxalines were obtained in high yields under optimal reaction conditions. This dual-protein method exhibited a regioselectivity higher than those of previously reported methods. This study not only provides a green and mild strategy for the synthesis of quinoxalines but also expands the application of lipase and hemoglobin in organic synthesis.
- Li, Fengxi,Li, Zhengqiang,Tang, Xuyong,Wang, Chunyu,Wang, Lei,Wang, Zhi,Xu, Yaning
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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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- Transition metal-free steric controlled one-pot synthesis of highly substituted N-amino 1,2,3-triazole derivatives via diazo transfer reaction from β-keto esters
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An efficient, simple protocol for the one-pot synthesis of N-amino 1,2,3-triazole from β-keto esters has been described. This method involves diazo transfer reaction into in situ generated hydrazones using imidazole sulfonyl azide as the nitrogen source.
- Nagarajan, Rajendran,Jayashankaran, Jayadevan,Emmanuvel, Lourdusamy
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- Rh-Catalyzed Coupling of Acrylic/Benzoic Acids with α-Diazocarbonyl Compounds: An Alternative Route for α-Pyrones and Isocoumarins
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A coupling of acrylic acids/benzoic acids with α-diazocarbonyl compounds has been realized by a combined catalytic system of rhodium catalyst and Zn(OAc)2 additive. The presence of Zn(OAc)2 obviously accelerates the C(sp2)
- Hong, Chao,Liu, Zhanxiang,Yu, Shuling,Zhang, Yuhong
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supporting information
p. 815 - 820
(2022/02/07)
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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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- Rhodium(III)-catalyzed chemodivergent annulations between phenyloxazoles and diazos via C–H activation
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Acid-controlled, chemodivergent and redox-neutral annulations for the synthesis of isocoumarins and isoquinolinones have been realized via Rh(III)-catalyzed C[sbnd]H activation. Diazo compounds act as a carbene precursor, and coupling occurs in one-pot process, where adipic acid and trimethylacetic acid promote chemodivergent cyclizations.
- Zhang, Xueguo,Wang, Peigen,Zhu, Liangwei,Chen, Baohua
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supporting information
p. 695 - 699
(2020/06/28)
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- Catalytic Ring Expansion of Activated Heteroarenes Enabled by Regioselective Dearomatization
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Catalytic ring expansion of activated heteroarenes through 1,4-dearomative addition of diazoacetates was established for the construction of various fused azepines by an elaborate control of the reaction kinetics at each step. The use of a silver catalyst was essential to drive the overall reaction for generating the desired seven-membered azepines. Because of the excellent substrate scope and selectivity, the developed methodology presents an innovative approach for the synthesis of multifused azepines, which are biologically relevant molecules.
- Kim, Jiyoung,Yoo, Eun Jeong
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supporting information
p. 4256 - 4260
(2021/06/28)
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- Rh(III)-Catalyzed [5 + 1] Annulation of Indole-enaminones with Diazo Compounds to Form Highly Functionalized Carbazoles
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A novel Rh(III)-catalyzed C-H activation/annulation cascade of indole-enaminones with diazo compounds was reported to construct diversely functionalized carbazole frameworks. The most notable characteristic is that this transformation could smoothly furnish a novel [5 + 1] cyclization product with good to excellent yields (up to 95%), accompanied by the thorough removal of acetyl and N,N-dimethyl groups of two substrates from the target products, rather than the normally expected [4 + 2] cyclization products.
- Jiang, Zhidong,Liu, Hong,Zhou, Jianhui,Zhou, Yu,Zhu, Haoran
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supporting information
p. 4406 - 4410
(2021/06/28)
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- Rhodium-Catalyzed [4+2] Annulation of N-Aryl Pyrazolones with Diazo Compounds To Access Pyrazolone-Fused Cinnolines
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An efficient synthesis of novel dinitrogen-fused heterocycles such as pyrazolo[1,2-a]cinnoline derivatives have been accomplished by the rhodium(III)-catalyzed reaction of N-arylpyrazol-5-ones with α-diazo compounds. This reaction proceeds through a cascade C?H activation/intramolecular cyclization with a broad substrate scope. Furthermore, this protocol is successfully extended to the unusual phosphorus-containing α-diazo compounds and cyclic diazo compounds as the cross-coupling partners to deliver the two new kinds of pyrazolo[1,2-a]cinnolinones. The control experiments were performed to reveal insight into the mechanism of this reaction, involving reversible C?H activation, migratory insertion of the diazo compound, and cascade cyclization as the key steps of the transformation. Moreover, gram-scale synthesis and further transformation of the target product demonstrate the synthetic utility of the present protocol.
- Lin, Chih-Yu,Huang, Wan-Wen,Huang, Ying-Ti,Dhole, Sandip,Sun, Chung-Ming
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supporting information
p. 4984 - 4992
(2021/09/28)
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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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- INHIBITORS OF HUMAN ATGL
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The present invention relates to novel inhibitors of adipose triglyceride lipase (ATGL) having an improved inhibitory activity against human ATGL (hATGL) as well as pharmaceutical compositions comprising these inhibitors, and their therapeutic use, particularly in the treatment or prevention of a lipid metabolism disorder, including, e.g., obesity, non-alcoholic fatty liver disease, type 2 diabetes, insulin resistance, glucose intolerance, hypertriglyceridemia, metabolic syndrome, cardiac and skeletal muscle steatosis, congenital generalized lipodystrophy, familial partial lipodystrophy, acquired lipodystrophy syndrome, atherosclerosis, or heart failure.
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Page/Page column 162-163
(2021/02/05)
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- Enantioselective Synthesis of Nitrogen-Nitrogen Biaryl Atropisomers via Copper-Catalyzed Friedel-Crafts Alkylation Reaction
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Nitrogen-nitrogen bonds containing motifs are ubiquitous in natural products and bioactive compounds. However, the atropisomerism arising from a restricted rotation around an N-N bond is largely overlooked. Here, we describe a method to access the first enantioselective synthesis of N-N biaryl atropisomers via a Cu-bisoxazoline-catalyzed Friedel-Crafts alkylation reaction. A wide range of axially chiral N-N bisazaheterocycle compounds were efficiently prepared in high yields with excellent enantioselectivities via desymmetrization and kinetic resolution. Heating experiments showed that the axially chiral bisazaheterocycle products have high rotational barriers.
- Guo, Chang-Qiu,Liu, Ren-Rong,Lu, Chuan-Jun,Wang, Xiao-Mei,Xu, Qi,Zhang, De-Bing,Zhang, Peng
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supporting information
p. 15005 - 15010
(2021/09/30)
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- Intramolecular Cyclization of Vinyldiazoacetates as a Versatile Route to Substituted Pyrazoles
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Vinyldiazo compounds undergo a thermal electrocyclization to form pyrazoles in yields of up to 95percent. The reactions are operationally simple, use readily available starting materials, require no intervention of a catalyst, and enable the synthesis of mono-, di- A nd tri-substituted pyrazoles. With the ability to produce highly substituted pyrazoles and the flexibility in installing various types of substituents, this method constitutes a new entry to this valuable heterocyclic scaffold and may be of interest to all branches of the chemical industry.
- Drikermann, Denis,G?rls, Helmar,Kerndl, Valerie,Vilotijevic, Ivan
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supporting information
p. 1158 - 1162
(2020/07/20)
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- Taking diazo transfer to water: α-diazo carbonyl compounds from in situ generated mesyl azide
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Mesyl azide generated in situ in aqueous medium converted a range of active methylene substrates into the corresponding diazo compounds in good yields and high purity with no need for chromatographic purification. The products thus obtained are suitable for the subsequent RhII-catalyzed O–H insertions with no need for chromatography in the interim.
- Dar'in, Dmitry V.,Krasavin, Mikhail,Shevalev, Robert M.,Zhmurov, Petr A.
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p. 372 - 373
(2020/06/19)
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- Crystal Structure and 1H NMR Experimental and Theoretical Study of Conformers of 5-Methyl-1-(4’-methylphenylsulfonylamino)-1H-[1,2,3]-triazole-4-carboxylic Acid Ethyl Ester and 5-Methyl-1-(phenylsulfonylamino)-1H-[1,2,3]-triazole-4-carboxylic A
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We reported experimental and theoretical investigation of conformers of 1,2,3-triazole derivatives, substances of exclusively synthetic origin, subject of extensive studies, because of several biological properties, such as antiviral, antimicrobial and an
- Campos, Vinicius R.,Carneiro, Jose W. M.,Cunha, Anna Claudia,Ferreira, Vitor F.,Freitas, Maria C. R.,Lage, Mateus R.,Resende, Jackson A. L. C.,Silva, Haroldo C.,da Silva, Marcos M. P.,de Almeida, Wagner B.,de Souza, Leonardo A.
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p. 867 - 885
(2020/10/14)
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- Ruthenium(II)-Catalyzed Ortho-C-H Alkylation of Naphthylamines with Diazo Compounds for Synthesis of 2,2-Disubstituted π-Extended 3-Oxindoles in Water
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Ruthenium(II)-catalyzed ortho-C-H alkylation of naphthylamines with diazo compounds for the synthesis of 2,2-disubstituted π-extended 3-oxindoles has been developed. The method represents the first example of C-H alkylation via carbenoid insertion in wate
- Wang, Xiaogang,Zhang, Jin,He, Yuan,Chen, Di,Wang, Chao,Yang, Fangzhou,Wang, Weitao,Ma, Yangmin,Szostak, Michal
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supporting information
p. 5187 - 5192
(2020/07/15)
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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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- On-Water Cp?Ir(III)-Catalyzed C-H Functionalization for the Synthesis of Chromones through Annulation of Salicylaldehydes with Diazo-Ketones
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A high-valent Ir(III)-catalyzed C-H bond functionalization is carried out for the first time on water for the synthesis of a biologically relevant chromone moiety. The C-H activation and annulation of salicylaldehydes with diazo-compounds provided the desired chromones. The synthesis of C3-substitution-free chromones has also been demonstrated by a one-pot decarboxylation by employing tert-butyl diazoester. C3 and C5 C-H activations of the product chromone are also carried out under different conditions for further diversification.
- Debbarma, Suvankar,Sk, Md Raja,Modak, Biswabrata,Maji, Modhu Sudan
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p. 6207 - 6216
(2019/05/24)
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- Synthesis and use of a cost-effective, aqueous soluble diazo transfer reagent – m-carboxybenzenesulfonyl azide
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Herein, we report the preparation and use of m-carboxybenzenesulfonyl azide as a diazo transfer reagent. This compound is an inexpensive and potentially scalable alternative to many of the diazo transfer reagents currently available, most of which have hazards associated with their use. Its usefulness and suitability as a diazo transfer reagent was assessed on the basis of cost, safety and its effectiveness in diazo transfer to a variety of different substrates.
- O'Mahony, Rosella M.,Broderick, Caoimhe M.,Lynch, Denis,Collins, Stuart G.,Maguire, Anita R.
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supporting information
p. 35 - 39
(2018/12/05)
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- Photocatalytic Alkylation of Pyrroles and Indoles with α-Diazo Esters
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This article describes the photoalkylation of electron-rich aromatic compounds with diazo esters. C-2-alkylated indoles and pyrroles are obtained with good yields even though the photocatalyst loading is as low as 0.075 mol %. For EWG-substituted substrates, the addition of a catalytic amount of N,N-dimethyl-4-methoxyaniline is required. Both EWG-EWG- and EWG-EDG-substituted diazo esters are suitable as alkylating agents. The reaction selectivity and mechanistic experiments suggest that carbenes/carbenoid intermediates are not involved in the reaction pathway.
- Ciszewski, Lukasz W.,Durka, Jakub,Gryko, Dorota
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supporting information
p. 7028 - 7032
(2019/09/12)
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- Oxazolinyl-Assisted Ru(II)-Catalyzed C?H Functionalization Based on Carbene Migratory Insertion: A One-Pot Three-Component Cascade Cyclization
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A rare, ruthenium-catalyzed, oxazolinlyl assisted C?H functionalization and three-component cascade cyclization for the synthesis of isoquinolinones via a metal-carbene migratory insertion is reported. The transformation is unique since it involves the fo
- Kumar, Gangam Srikanth,Khot, Nandkishor Prakash,Kapur, Manmohan
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supporting information
p. 73 - 78
(2018/12/11)
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- Rh(III)-catalyzed annulation of BOC-protected benzamides with diazo compounds: Approach to isocoumarins
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A mild rhodium-catalyzed annulation of Boc-protected benzamides with diazo compounds via C?C/C?O bond formation has been explored. In the presence of [Cp*RhCl2]2, AgSbF6 and Cs2CO3, Boc-protected benzamides can be effectively annulated to yield isocoumarins in 0.5–2 h.
- Dong, Guangyu,Li, Chunpu,Liu, Hong
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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(III)-catalyzed [4+2] annulation via C-H activation: Synthesis of multi-substituted naphthalenone sulfoxonium ylides
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A convenient Rh(III)-catalyzed C-H activation and cascade [4+2] annulation for the synthesis of naphthalenone sulfoxonium ylides has been developed. This method features perfect regioselectivity, mild and redox-neutral reaction conditions, and broad substrate tolerance with good to excellent yields. Preliminary mechanistic experiments were conducted and a plausible reaction mechanism was proposed. The new type naphthalenone sulfoxonium ylides could be further transformed into multi-substituted naphthols, which demonstrates the practical utility of this methodology.
- Song, Xiaohan,Han, Xu,Zhang, Rui,Liu, Hong,Wang, Jiang
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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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- [Cp*RhIII] in an Ionic Liquid as a Highly Efficient and Recyclable Catalytic Medium for Regio- and Diastereoselective Csp3–H Carbenoid Insertion
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Reported herein is a bidentate-assisted Csp3–H bond insertion using Cp*RhIII/IL as a highly efficient and recyclable catalytic medium, while showing good functional group tolerance. Notably, the application of ionic liquid not only lowered the temperature, but also enhanced the diastereoselectivity of this reaction. This work significantly expanded the scope of ionic liquids in Csp3–H functionalizations.
- Li, Jianglian,Zhou, Lin,Wang, Yaoling,Ma, Qiang,Lei, Yuan,Lai, Ruizhi,Luo, Yi,Hai, Li,Wu, Yong
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supporting information
p. 7448 - 7451
(2019/11/28)
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- β-(Cycloalkylamino)ethanesulfonyl azides as novel water-soluble reagents for the synthesis of diazo compounds and heterocycles
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[Figure not available: see fulltext.] Novel water-soluble sulfonyl azides were synthesized, which are basic by nature. The obtained compounds were used as donors of the diazo group in the diazo transfer reaction. Due to their good solubility in water and high polarity, the byproducts formed in this case were easily separated from the desired products by washing with water or column chromatography. It was also shown that new sulfonyl azides as a result of reactions can be incorporated in heterocyclic products, imparting them water solubility.
- Shafran, Yuri M.,Silaichev, Pavel S.,Bakulev, Vasiliy A.
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p. 1251 - 1261
(2020/01/11)
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- Rapid Assembly of Saturated Nitrogen Heterocycles in One-Pot: Diazo-Heterocycle “Stitching” by N–H Insertion and Cyclization
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Methods that provide rapid access to new heterocyclic structures in biologically relevant chemical space provide important opportunities in drug discovery. Here, a strategy is described for the preparation of 2,2-disubstituted azetidines, pyrrolidines, pi
- Boddy, Alexander J.,Affron, Dominic P.,Cordier, Christopher J.,Rivers, Emma L.,Spivey, Alan C.,Bull, James A.
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supporting information
p. 1458 - 1462
(2019/01/04)
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- On-Water Cp?Ir(III)-catalyzed C-H functionalization for the synthesis of chromones through annulation of salicylaldehydes with diazo-ketones
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A high-valent Ir(III)-catalyzed C-H bond functionalization is carried out for the first time on water for the synthesis of a biologically relevant chromone moiety. The C-H activation and annulation of salicylaldehydes with diazo-compounds provided the desired chromones. The synthesis of C3-substitution-free chromones has also been demonstrated by a one-pot decarboxylation by employing tert-butyl diazoester. C3 and C5 C-H activations of the product chromone are also carried out under different conditions for further diversification.
- Debbarma, Suvankar,Sk, Md Raja,Modak, Biswabrata,Maji, Modhu Sudan
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- Mechanistic Study of In Situ Generation and Use of Methanesulfonyl Azide as a Diazo Transfer Reagent with Real-Time Monitoring by FlowNMR
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The mechanistic pathway by which the hazardous diazo transfer reagent methanesulfonyl azide can be formed in situ, from methanesulfonyl chloride and aqueous sodium azide, has been investigated using real-time reaction monitoring by FlowNMR. In the presence of triethylamine, rapid generation of methanesufonyl azide is observed, via a mechanistic pathway consistent with involvement of a sulfene or methanesulfonyl triethylammonium intermediate. Accordingly, it is possible to generate and use methanesulfonyl azide in a single synthetic step for a diazo transfer process.
- Lynch, Denis,O'Mahony, Rosella M.,McCarthy, Daniel G.,Bateman, Lorraine M.,Collins, Stuart G.,Maguire, Anita R.
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supporting information
p. 3575 - 3580
(2019/06/08)
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- Intrinsically Safe and Shelf-Stable Diazo-Transfer Reagent for Fast Synthesis of Diazo Compounds
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We report a crystalline compound 2-azido-4,6-dimethoxy-1,3,5-triazine (ADT) as an intrinsically safe, highly efficient, and shelf-stable diazo-transfer reagent. Because the decomposition of ADT is an endothermal process (ΔH = 30.3 kJ mol-1), ADT is intrinsically nonexplosive, as proved by thermal, friction, and impact tests. The diazo-transfer reaction based on ADT gives diazo compounds in excellent yields within several minutes at room temperature. ADT is very stable upon >1 year storage under air at room temperature.
- Xie, Shibo,Yan, Ziqiang,Li, Yuanheng,Song, Qun,Ma, Mingming
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p. 10916 - 10921
(2018/09/17)
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- Three-Component Ring-Opening Reactions of Cyclic Ethers, α-Diazo Esters, and Weak Nucleophiles under Metal-Free Conditions
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A protocol for three-component reactions of cyclic ethers, α-diazo esters, and weak nitrogen, oxygen, carbon, and sulfur nucleophiles (pKa = 2.2-14.8) to afford a variety of structurally complex α-oxyalkylated esters is reported. These reactions involve intermolecular activation of the cyclic ether (present in excess) by the α-diazo ester to form an oxonium ylide under metal-free conditions, followed by ring opening by the nucleophile.
- Lu, Lin,Chen, Chuwei,Jiang, Huanfeng,Yin, Biaolin
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p. 14385 - 14395
(2018/11/27)
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- Method for synthesizing alpha-diazoesters compound by using microwave at normal pressure
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The invention discloses a method for synthesizing an alpha-diazoesters compound by using microwave at normal pressure. An esters compound and P-toluenesulfonyl azide are used as initial raw materials,1,8-diazabicyclo[5.4.0]undec-7-ene(DBU) is used as a catalyst, the alpha-diazoesters compound can be generated in 30 minutes by virtue of a diazo transfer reaction under a microwave assisting heating condition, and the alpha-diazoesters compound can further generate a functional product. The organic reaction rate of the method is multiple times faster than the traditional heating method, the reaction efficiency is high, the operation is simple and convenient, the synthetic reaction condition is mild, the product type is rich, and the functional group is diversified.
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Paragraph 0068-0070
(2018/11/22)
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- Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds
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Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular SN2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.
- Li, Siqi,Chen, Xingpeng,Xu, Jiaxi
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supporting information
p. 1613 - 1620
(2018/03/07)
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- Rh(III)-Catalyzed C-H Activation of Benzoylacetonitriles and Tandem Cyclization with Diazo Compounds to Substituted Benzo [de] chromenes
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Rh (III)-catalyzed C-H activation of benzoylacetonitriles in coupling with diazo compounds was developed to synthesize diversified substituted benzo[de]chromenes via a formal (4 + 2) cycloaddition with a diazo compound and subsequent tandem (4 + 2) cycloa
- Fang, Feifei,Zhang, Chunmei,Zhou, Chaofan,Li, Yazhou,Zhou, Yu,Liu, Hong
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supporting information
p. 1720 - 1724
(2018/04/14)
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- Rhodium(I)-Catalyzed Coupling-Cyclization of C=O Bonds with α-Diazoketones
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An unprecedented intermolecular nucleophilic attack of C=X bonds (X = O and S) on the rhodium(I)-carbenes has been developed. This transformation allows for the coupling-cyclization of aroylamides with α-diazoketones and provides concise access to 2,4,5-trisubstituted 1,3-oxazoles and 1,3-thiazoles with a broad tolerance of functional groups.
- Chen, Ziyang,Hu, Xinwei,Huang, Junmin,Zeng, Wei
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supporting information
p. 3980 - 3983
(2018/07/15)
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- Catalytic Enantioselective Cloke–Wilson Rearrangement
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Racemic cyclopropyl ketones undergo enantioselective rearrangement to deliver the corresponding dihydrofurans in the presence of a chiral phosphoric acid as the catalyst. The reaction involves activation of the donor-acceptor cyclopropane substrate by the
- Ortega, Alesandere,Manzano, Rubén,Uria, Uxue,Carrillo, Luisa,Reyes, Efraim,Tejero, Tomas,Merino, Pedro,Vicario, Jose L.
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supporting information
p. 8225 - 8229
(2018/06/29)
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- Cyclopentene Annulations of Alkene Radical Cations with Vinyl Diazo Species Using Photocatalysis
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A direct (3+2) cycloaddition between alkenes and vinyl diazo reagents using either Cr or Ru photocatalysis is described. The intermediacy of a radical cation species enables a nucleophilic interception by vinyl diazo compounds, a departure from their trad
- Sarabia, Francisco J.,Li, Qiankun,Ferreira, Eric M.
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supporting information
p. 11015 - 11019
(2018/07/30)
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- Synthesis of 1 H-Pyrrol-3(2 H)-ones via Three-Component Reactions of 2,3-Diketo Esters, Amines, and Ketones
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An efficient one-pot, three-component reaction of 2,3-diketo esters with amines and ketones has been developed for the synthesis of 1H-pyrrol-3(2H)-ones. By using trifluoroacetic acid (TFA) as the additive and acetonitrile (MeCN) as the solvent, this conv
- Sha, Qiang,Wang, Junke,Doyle, Michael P.
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p. 11288 - 11297
(2018/09/12)
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- Amine-mediated synthesis of amides from 1,3-dicarbonyl compounds through a domino diazo transfer/aminolysis process
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The dual role of amines as both catalysts and substrates for the synthesis of diazo compounds or carboxamides from 1,3-dicarbonyl compounds is described herein. In the presence of a suitable diazo transfer agent, primary and cyclic secondary amines act as basic catalysts for the diazo transfer reaction to malonates, β-keto esters, and β-diketones. Depending on the structure of the 1,3-dicarbonyl compound and the nucleophilicity of the amine, the resulting α-diazo-β-keto ester undergoes cleavage of the acyl group to give amides. A multifunctionalized γ-azido-α-diazo-β-keto ester was cleanly prepared in good yields by this one-pot protocol under practical and safe conditions, being employed in a Knoevenagel-type condensation with aromatic aldehydes to give densely functionalized diazo azido compounds. Further treatment of these unsaturated γ-azido-α-diazo-β-keto esters with primary amines readily furnished the corresponding α-azidocinnamamides in high yields, which were used in the synthesis of novel indole-2-carboxamides through the rhodium-catalyzed intramolecular C–H insertion.
- Costin, Taíssa A.,Dutra, Luiz G.,Bortoluzzi, Adailton J.,Sá, Marcus M.
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p. 4549 - 4559
(2017/07/11)
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- Ruthenium Complexes Immobilized on Functionalized Knitted Hypercrosslinked Polymers as Efficient and Recyclable Catalysts for Organic Transformations
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A hypercrosslinked polymer (HCP)-immobilized ruthenium catalyst (HCP–PPh3–Ru) was prepared from benzene and triphenylphosphine (PPh3) through a one-step external cross-linking reaction. The structure and composition of the catalyst were fully characterized by many physicochemical methods. HCP–PPh3–Ru was found to possess high Brunauer–Emmett–Teller (BET) surface area, large pore volume, and low skeletal density. Moreover, the Ru catalyst was also featured some advantages, such as low synthetic cost and good chemical and thermal stability. HCP–PPh3–Ru was then used as a recoverable and effective catalyst for the synthesis of 2,4-diaryl-substituted pyridines from acetophenones, ammonium acetate (NH4OAc) and dimethylformamide (DMF), and the cycloaddition reaction of diazodicarbonyl compounds with olefins to afford dihydrofurans. In addition, a combination of HCP–PPh3–Ru and Amberlyst-15 enabled us to establish a simple protocol for the direct synthesis of carbazole derivatives from diazodicarbonyl compound, alkyl vinyl ether and indole. In these selected reactions, the catalyst was easily recovered and reused several times without significant activity loss. (Figure presented.).
- Jia, Zhifang,Wang, Kewei,Tan, Bien,Gu, Yanlong
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supporting information
p. 78 - 88
(2017/01/14)
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- Synthesis of 3-acyl-5,6-dihydro-1,4-oxathiines through ring expansion of thiiranes
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Synthesis of 3-acyl-5,6-dihydro-1,4-oxathiines has been achieved via reactions of thiiranes and α-diazo-β-1,3-dicarbonyl compounds under microwave and copper sulfate-assisted conditions. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-1,4-oxathiines from readily available thiiranes and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes. The reaction mechanism was also proposed.
- Chen, Xingpeng,Xu, Jiaxi
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supporting information
p. 1651 - 1654
(2017/04/04)
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- Rh(III)-Catalyzed Regio- and Chemoselective [4 + 1]-Annulation of Azoxy Compounds with Diazoesters for the Synthesis of 2H-Indazoles: Roles of the Azoxy Oxygen Atom
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A Rh(III)-catalyzed tandem C-H alkylation/intramolecular decarboxylative cyclization of azoxy compounds with diazoesters for the synthesis of 3-acyl-2H-indazoles is disclosed. The azoxy instead of the azo group enables a distinct approach for cyclative capture, leading to a [4 + 1]-annulation rather than a classic [4 + 2] manner. The azoxy oxygen atom is traceless after annulation, and further removal from the product is not required. This reaction features a complete regioselectivity for unsymmetrical azoxybenzenes and a compatibility of monoaryldiazene oxides.
- Long, Zhen,Wang, Zhigang,Zhou, Danni,Wan, Danyang,You, Jingsong
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supporting information
p. 2777 - 2780
(2017/06/07)
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- One-pot synthesis of 2,3-difunctionalized indoles: Via Rh(III)-catalyzed carbenoid insertion C-H activation/cyclization
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Reported herein is the first Rh(iii)-catalyzed carbenoid insertion C-H activation/cyclization of N-arylureas and α-diazo β-keto esters. The redox-neutral reaction has the following features: good to excellent yields, broad substrate/functional group tolerance, exclusive regioselectivity, and no need for additional oxidants or additives, which render this methodology as a more efficient and versatile alternative to the existing methods for the synthesis of 2,3-difunctionalized indoles.
- Lv, Honggui,Shi, Jingjing,Wu, Bo,Guo, Yujuan,Huang, Junjun,Yi, Wei
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supporting information
p. 8054 - 8058
(2017/10/13)
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- Synthesis of 2,3-Disubstituted NH Indoles via Rhodium(III)-Catalyzed C-H Activation of Arylnitrones and Coupling with Diazo Compounds
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A rhodium-catalyzed intermolecular coupling between arylnitrones and diazo compounds by C-H activation/[4 + 1] annulation with a C(N2)-C(acyl) bond cleavage is reported, and 2,3-disubstituted NH indoles are directly synthesized in up to a 94% yield. A variety of functional groups are applicable to this reaction to give the corresponding products with high selectivity. Compared to other previously reported Rh(III)-catalyzed synthesis of homologous series, this method is simpler, more general, and more efficient.
- Guo, Xin,Han, Jianwei,Liu, Yafeng,Qin, Mingda,Zhang, Xueguo,Chen, Baohua
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p. 11505 - 11511
(2017/11/10)
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- Exploiting the Continuous in situ Generation of Mesyl Azide for Use in a Telescoped Process
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The hazardous diazo transfer reagent mesyl azide has been safely generated and used in situ for continuous diazo transfer as part of an integrated synthetic process with an embedded safety quench. Diazo transfer to β-keto esters and a β-ketosulfone was successful. In-line phase separation, by means of a continuous liquid–liquid separator, enabled direct telescoping with a thermal Wolff rearrangement.
- O'Mahony, Rosella M.,Lynch, Denis,Hayes, Hannah L. D.,Ní Thuama, Eilís,Donnellan, Philip,Jones, Roderick C.,Glennon, Brian,Collins, Stuart G.,Maguire, Anita R.
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p. 6533 - 6539
(2017/10/24)
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- Iridium-Catalysed Cascade Synthesis of Oxindoles Using Diazo Compounds: A Quick Entry to C-7-Functionalized Oxindoles
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A cascade iridium-catalysed oxindole synthesis was achieved using pyridyl-protected anilines and bis(2,2,2-trifluoroethyl) 2-diazomalonate. The developed protocol is simple and scalable, and has a broad scope and excellent regioselectivity. The pyridyl directing group can easily be removed. The method was further extended to give C-7-functionalized oxindole derivatives in a straightforward manner. The role of bis(2,2,2-trifluoroethyl) 2-diazomalonate for oxindole preparation has been explored.
- Karmakar, Ujjwal,Das, Debapratim,Samanta, Rajarshi
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p. 2780 - 2788
(2017/05/29)
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- Six-Membered Cyclic Nitroso Acetals: Synthesis and Studies of the Nitrogen Inversion Process of N-Silyloxy-3,6-dihydro-2H-1,2-oxazines
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Silyl nitronates undergo rhodium-catalyzed formal [3+3]-cycloaddition with enol diazoacetates to form N-silyloxy-3,6-dihydro-2H-1,2-oxazines. The scope of the reaction and the extent of the major side process were evaluated. A mechanistic scheme was propo
- Shved, Alexander S.,Tabolin, Andrey A.,Novikov, Roman A.,Nelyubina, Yulia V.,Timofeev, Vladimir P.,Ioffe, Sema L.
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supporting information
p. 5569 - 5578
(2016/11/25)
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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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- Rh(iii)-catalyzed relay carbenoid functionalization of aromatic C-H bonds: Access to π-conjugated fused heteroarenes
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A novel Rh(iii)-catalyzed relay cross-coupling/cyclization cascade between arylketoimines and diazoesters is described. This transformation provides a concise access to unique π-conjugated 1-azaphenalenes (1-APLEs) via a double aryl Csp2-H bond
- Xie, Ying,Chen, Xun,Liu, Xin,Su, Shi-Jian,Li, Jianzhang,Zeng, Wei
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supporting information
p. 5856 - 5859
(2016/05/19)
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- Studies towards a greener diazo transfer methodology
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A very mild, efficient and green method has been developed for diazo transfer to a range of β-ketoesters using polystyrene-supported benzenesulfonyl azide, water as solvent and a catalytic amount of base. This methodology eliminates the need for a standard work up and purification which is usually required to remove the sulfonamide by-product from the reaction.
- Tarrant, Elaine,O'Brien, Claire V.,Collins, Stuart G.
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p. 31202 - 31209
(2016/04/09)
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