- Br?nsted Acid Catalyzed (4 + 2) Cyclocondensation of 3-Substituted Indoles with Donor-Acceptor Cyclopropanes
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Acylcyclopropanes are employed as useful donor-acceptor cyclopropanes that undergo formal (4 + 2) cyclocondensation with N-unprotected 3-substituted indoles in the presence of a Br?nsted acid catalyst. The reaction involves the simultaneous alkylation of both the N and C-2 positions of the indole and provides access to the 8,9-dihydropyrido[1,2-a]indole scaffold that is the central core of several biologically relevant indole alkaloids in excellent yields and good selectivities.
- Ortega, Alesandere,Uria, Uxue,Tejero, Tomás,Prieto, Liher,Reyes, Efraim,Merino, Pedro,Vicario, Jose L.
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- Metalation of α-diazocarbonyl compounds using Grignard reagents. A convenient synthesis of α-diazo-β-ketoesters and mixed esters of α-diazomalonate
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α-Diazocarbonyl compounds react with methylmagnesium bromide at -78°C generating the corresponding α-diazo-α-bromomagnesio species, which can be intercepted by various electrophilic reagents. For example, with alkyl chloroformates α-diazo-β-ketoesters or mixed esters of α-diazomalonate are obtained in good yields.
- Cuevas-Ya?ez, Erick,Muchowski, Joseph M.,Cruz-Almanza, Raymundo
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- Rhodium(III)-catalyzed C-C bond formation of quinoline N-oxides at the C-8 position under mild conditions
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The Rh(III)-catalyzed C-8 selective direct alkylation and alkynylation of quinoline N-oxides has been developed. The reactions proceeded highly efficiently at room temperature over a broad range of substrates with excellent regioselectivity and functional group tolerance. This development demonstrates the synthetic utility of the N-oxide directing group as a stepping stone for remote C-H functionalization of quinolines.
- Jeong, Jisu,Patel, Pitambar,Hwang, Heejun,Chang, Sukbok
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- Acetoxy-Substituted Cyclopropane Dicarbonyls as Stable Donor-Acceptor-Acceptor Cyclopropanes
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A study of cyclopropanations of oxy-substituted ethenes with ethyl α-aroyl-α-diazoacetates is described. The reaction of ethyl α-aroyl-α-diazoacetates with trimethylsilyl vinyl ether or ethyl vinyl ether gave dihydrofuran products, but when vinyl acetate
- Reyes, Yahaira,Mead, Keith T.
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Read Online
- 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
(2022/01/12)
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- Sulfur-controlled and rhodium-catalyzed formal (3 + 3) transannulation of thioacyl carbenes with alk-2-enals and mechanistic insights
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A rhodium-catalyzed denitrogenative formal (3 + 3) transannulation of 1,2,3-thiadiazoles with alk-2-enals is achieved, producing 2,3-dihydrothiopyran-4-ones in moderate to excellent yields. An inverse KIE of 0.49 is obtained, suggesting the reversibility of the oxidative addition of thioacyl Rh(i) carbenes to alk-2-enals. The late-stage structural modifications of steroid compounds are realized. Moreover, our studies show that thioacyl carbenes have different reactivities to those of α-oxo and α-imino carbenes, and highlight the importance of heteroatoms in deciding the reactivities of heterovinyl carbenes.
- Wu, Qiuyue,Dong, Ziyang,Xu, Jiaxi,Yang, Zhanhui
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p. 3173 - 3180
(2021/04/21)
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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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- 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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p. 8694 - 8698
(2021/11/24)
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- Design, synthesis and anticancer activity of 5-aryl-4-(4-arylpiperazine-1-carbonyl)-1,2,3-thiadiazoles as microtubule-destabilizing agents
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Hereby, we report our efforts on discovery and optimization of a new series of 5-aryl-4-(4-arylpiperazine-1-carbonyl)-1,2,3-thiadiazoles as new microtubule-destabilizing agents along our previous study. Guided by docking model analysis, we introduced the 1,2,3-thiadiazole moiety containing the hydrogen-bond acceptors as B-ring of XRP44X analogues. Extensive structure modifications were performed to investigate the detailed structure and activity relationships (SARs). Some compounds exhibited potent antiproliferative activities against three human cancer cell lines (SGC-7901, A549 and HeLa). The compound 5m exhibited the highest potency against the three cancer cell lines. The tubulin polymerization experiments indicated that compound 5m effectively inhibited the tubulin polymerization, and immunostaining assay revealed that it significantly disrupted microtubule dynamics. Moreover, cell cycle studies revealed that compound 5m dramatically arrested cell cycle progression at G2/M phase.
- Wang, Chao,Wang, Zeyu,Gao, Minghuan,Li, Yuelin,Zhang, Yujing,Bao, Kai,Wu, Yingliang,Guan, Qi,Zuo, Daiying,Zhang, Weige
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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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- 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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- 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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- 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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- Stereoselective bioreduction of α-diazo-β-keto esters
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Diazo compounds are versatile reagents in chemical synthesis and biology due to the tunable reactivity of the diazo functionality and its compatibility with living systems. Much effort has been made in recent years to explore their accessibility and synth
- Costin, Taíssa A.,González-Granda, Sergio,Gotor-Fernández, Vicente,Sá, Marcus M.
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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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- 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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- 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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- Atroposelective Phosphoric Acid Catalyzed Three-Component Cascade Reaction: Enantioselective Synthesis of Axially Chiral N-Arylindoles
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An efficient organocatalytic atroposelective three-component cascade reaction of 2,3-diketoesters, aromatic amines, and 1,3-cyclohexanediones has been developed for the highly enantioselective synthesis of axially chiral N-arylindoles. The success of this method derives from the use of a newly developed second-generation chiral spirocyclic phosphoric acid as the catalyst. In addition, this protocol was extended to the synthesis of an axially chiral monophosphorus ligand.
- Wang, Lei,Zhong, Jialing,Lin, Xufeng
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supporting information
p. 15824 - 15828
(2019/10/28)
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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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- 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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- 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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- 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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- 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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- Copper-catalyzed chemoselective cross-coupling reaction of thioamides and α-diazocarbonyl compounds: Synthesis of enaminones
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The development of operationally simple and cost-effective methods for C[sbnd]C bond formation reactions are highly important in pharmaceutical, agrochemical and material research. In this article we describe the first copper-catalyzed cross-coupling reaction of thioamides with acceptor/acceptor-substituted and acceptor-only substituted α-diazocarbonyl compounds to yield enaminones. The reaction shows broad substrate scope in terms of thioamides and diazocarbonyl compounds. Primary, secondary and tertiary thioamides all give enanminones when reacted with α-diazodiesters, α-diazoketoesters, α-diazodiketones, α-diazoketoamides, α-diazoesteramides, α-diazoketosulfones and α-diazomonoketones.
- Pal, Arpal,Koduri, Naga D.,Wang, Zhiguo,Quiroz, Erika Lopez,Chong, Alexandra,Vuong, Matthew,Rajagopal, Nisha,Nguyen, Michael,Roberts, Kenneth P.,Hussaini, Syed R.
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supporting information
p. 586 - 589
(2017/01/16)
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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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- 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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- 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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- Regioselective Synthesis of Dihydrothiophenes and Thiophenes via the Rhodium-Catalyzed Transannulation of 1,2,3-Thiadiazoles with Alkenes
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A method for the regioselective synthesis of a wide range of dihydrothiophenes was developed from the rhodium-catalyzed transannulation of 1,2,3-thiadiazoles with aliphatic, aromatic, and heteroaromatic alkenes. Tandem rhodium-catalyzed transannulation of 1,2,3-thiadiazoles with alkenes followed by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) oxidation was also demonstrated for the one-pot regioselective synthesis of various thiophenes. Advantages of the present method include a broad substrate scope, wide functional group compatibility, and high regioselectivity.
- Son, Jeong-Yu,Kim, Jonghye,Han, Sang Hoon,Kim, Sung Hong,Lee, Phil Ho
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p. 5408 - 5411
(2016/11/06)
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- C-H Activation-Based Traceless Synthesis via Electrophilic Removal of a Directing Group. Rhodium(III)-Catalyzed Entry into Indoles from N-Nitroso and α-Diazo-β-keto Compounds
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A distinct C-H activation-based traceless synthetic protocol via electrophilic removal of a directing group is reported, complementing the currently exclusively used nucleophilic strategy. Rh(III)-catalyzed, N-nitroso-directed C-H activation allows the development of a traceless, atom- and step-economic, cascade approach for the synthesis of indole skeletons, starting from readily available N-nitroso and α-diazo-β-keto compounds. Importantly, the cyclization/denitrosation reaction represents a hitherto unobserved reactivity pattern for the N-nitroso group.
- Wang, Jie,Wang, Mingyang,Chen, Kehao,Zha, Shanke,Song, Chao,Zhu, Jin
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supporting information
p. 1178 - 1181
(2016/03/15)
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- Taming tosyl azide: The development of a scalable continuous diazo transfer process
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Heat and shock sensitive tosyl azide was generated and used on demand in a telescoped diazo transfer process. Small quantities of tosyl azide were accessed in a 'one pot' batch procedure using shelf stable, readily available reagents. For large scale diaz
- Deadman, Benjamin J.,O'Mahony, Rosella M.,Lynch, Denis,Crowley, Daniel C.,Collins, Stuart G.,Maguire, Anita R.
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supporting information
p. 3423 - 3431
(2016/04/09)
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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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- Controllable Rh(III)-Catalyzed Annulation between Salicylaldehydes and Diazo Compounds: Divergent Synthesis of Chromones and Benzofurans
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A Rh(III)-catalyzed annulation between salicylaldehydes and diazo compounds with controllable chemoselectivity is described. AgNTf2 favored benzofurans via a tandem C-H activation/decarbonylation/annulation process, while AcOH led to chromones through a C-H activation/annulation pathway. The reaction exhibited good functional group tolerance and scalability. Moreover, only a single regioisomer of benzofuran was obtained due to the in situ decarbonylation orientation effect.
- Sun, Peng,Gao, Shang,Yang, Chi,Guo, Songjin,Lin, Aijun,Yao, Hequan
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supporting information
p. 6464 - 6467
(2016/12/23)
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- Asymmetric synthesis of 1H-pyrrol-3(2H)-ones from 2,3-diketoesters by combination of aldol condensation with benzilic acid rearrangement
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An efficient two-step protocol for the asymmetric synthesis of 1H-pyrrol-3(2H)-one derivatives in 99% ee from conveniently accessed 2,3-diketoesters has been developed.
- Sha, Qiang,Arman, Hadi,Doyle, Michael P.
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supporting information
p. 108 - 111
(2015/12/26)
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- Rh(III)-Catalyzed Redox-Neutral Annulation of Primary Benzamides with Diazo Compounds: Approach to Isoquinolinones
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Reported herein is a Rh-catalyzed redox-neutral annulation of primary benzamides with diazo compounds, representing an efficient and economic protocol to isoquinolinones. The procedure exhibited good functional group tolerability, scalability, and regioselectivity, obviating the need for oxidants, and only environmentally benign N2 and H2O were released. Further utilization of the method provided an alternative route to functionalized isoquinolines.
- Wu, Youzhi,Sun, Peng,Zhang, Kaifan,Yang, Tie,Yao, Hequan,Lin, Aijun
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p. 2166 - 2173
(2016/03/15)
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- Rhodium Thiavinyl Carbenes from 1,2,3-Thiadiazoles Enable Modular Synthesis of Multisubstituted Thiophenes
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The rhodium-catalyzed transannulation reaction between 1,2,3-thiadiazoles and alkynes, proceeding via intermediacy of the previously unknown Rh thiavinyl carbene, toward a highly efficient and regioselective synthesis of up to fully substituted thiophenes is described.
- Kurandina, Daria,Gevorgyan, Vladimir
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supporting information
p. 1804 - 1807
(2016/05/19)
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- Copper-Catalyzed Regioselective Cascade Alkylation and Cyclocondensation of Quinoline N-Oxides with Diazo Esters: Direct Access to Conjugated π-Systems
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An inexpensive copper-catalyzed cascade regioselective alkylation, followed by cyclocondensation of quinoline N-oxides with α-diazo esters has been achieved successfully to provide heteroarene-containing conjugated π-systems. The developed method is simple, straightforward, and economical with a broad range of substrate scope. The dual role of copper catalyst in the C?H bond functionalization and in Lewis acid-promoted cyclization was explored.
- Biswas, Aniruddha,Karmakar, Ujjwal,Pal, Arun,Samanta, Rajarshi
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supporting information
p. 13826 - 13830
(2016/09/21)
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- Synthesis of α-diazo-β-keto esters, phosphonates and sulfones via acylbenzotriazole-mediated acylation of a diazomethyl anion
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We report a method for the synthesis of α-diazo-β-keto esters, phosphonates and sulfones via acylation of corresponding diazomethyl anions with N-acylbenzotriazoles. The N-o-amino-acylbenzotriazoles exhibited an unprecedented transphosphorylation reaction
- Pramanik, Mukund M. D.,Rastogi, Namrata
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supporting information
p. 11567 - 11571
(2015/12/04)
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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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supporting information
p. 15328 - 15331
(2015/10/20)
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- Synthesis of Heterocycle-fused Pyridine N-Oxides from Oximes and Diazo Compounds via RhIII-Catalyzed C-H Activation and Annulation
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A RhIII-catalyzed tandem C-H activation and C-N bond formation reaction between oximes and diazo compounds for the synthesis of heterocycle-fused pyridine N-oxides has been developed. The reaction exhibits good functional group tolerance and regioselectivity. After simple transformation, the 1-substituted, 1,3-disubstituted, 1,4-disubstituted and 1,3,4-trisubstituted heterocycle-fused pyridines were all obtained in high efficiency. Moreover, this strategy has also been expanded to the synthesis of a key intermediate for the construction of one potential anti-HIV agent.
- Sun, Peng,Wu, Youzhi,Yang, Tie,Wu, Xiaoming,Xu, Jinyi,Lin, Aijun,Yao, Hequan
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supporting information
p. 2469 - 2473
(2015/08/18)
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- Synthesis of Aryldiazoacetates through Palladium(0)-Catalyzed Deacylative Cross-Coupling of Aryl Iodides with Acyldiazoacetates
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Palladium(0)-catalyzed deacylative cross-coupling of aryl iodides and acyldiazocarbonyl compounds can be achieved at room temperature under mild reaction conditions. The coupling reaction represents a highly efficient and general method for the synthesis of aryldiazocarbonyl compounds, which have found wide and increasing applications as precursors for generating donor/acceptor-substituted metallocarbenes.
- Ye, Fei,Wang, Chengpeng,Zhang, Yan,Wang, Jianbo
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supporting information
p. 11625 - 11628
(2016/02/19)
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- Two-stage synthesis of 3-(perfluoroalkyl)-substituted vinyldiazocarbonyl compounds and their nonfluorinated counterparts: A comparative study
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Two approaches for the synthesis of fluorinated (F) and nonfluorinated (H) 4-(alkoxycarbonyl)-substituted cis- and trans-vinyldiazocarbonyl compounds with substituents of variable stereoelectronic nature (H, Me, Ph, CF3, OTBS) at the C-3 atom of the vinyl double bond from the relevant 1,3-dicarbonyl compounds were compared: a pathway using the Wittig reaction followed by a diazo transfer reaction was most efficient for the synthesis of the H-vinyldiazocarbonyl compounds (total yields of up to 60%), while the yields of their F-analogues under similar conditions did not exceed 16-37%. An approach via diazo transfer followed by the Wittig reaction, in contrast, is more effective for the preparation of F-vinyldiazocarbonyl compounds (total yields 37-69%). The configuration of the resulting F- and H-vinyldiazocarbonyl compounds is evidently controlled by the steric bulk of the substituent at the C-3 atom of the vinyl double bond and, in addition, depends on the specific synthetic pathway. Georg Thieme Verlag Stuttgart . New York.
- Supurgibekov, Murat B.,Prakash, G.K. Surya,Nikolaev, Valerij A.
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p. 1215 - 1226
(2013/06/04)
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- Development of the enantioselective addition of ethyl diazoacetate to aldehydes: Asymmetric synthesis of 1,2-diols
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A novel synthetic strategy toward the asymmetric synthesis of vicinal diols bearing a tertiary center is presented. The method encompasses the dinuclear Mg-catalyzed asymmetric addition of ethyl diazoacetate into several aldehydes, oxidation of the diazo functionality, and diastereoselective alkyl transfer of various organometallics into the resulting chiral β-hydroxy-α- ketoesters to afford a diverse range of 1,2-diols in high yield, diastereoselectivity, and chirality transfer.
- Trost, Barry M.,Malhotra, Sushant,Koschker, Philipp,Ellerbrock, Pascal
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p. 2075 - 2084
(2012/03/12)
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- OXAZOLE AND THIAZOLE DERIVATIVES AS ALX RECEPTOR AGONISTS
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The invention relates to oxazole and thiazole derivatives of formula (I), wherein A, E, X, R1 and R2 are as defined in the description, their preparation and their use as pharmaceutically active compounds.
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Page/Page column 35
(2012/05/20)
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- Nucleophilic fluorination of β-ketoester derivatives with HBF 4
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Treating readily available α-diazo-β-ketoesters with HBF 4 results in nucleophilic fluorination by the usually inert and stable tetrafluoroborate anion. The resulting α-fluoro-β-ketoesters are highly versatile synthetic intermediates, for example in the preparation of fluoro-heterocycles, as illustrated by the direct formation of fluoro-pyrimidines, -pyrazoles and -coumarins in a single step.
- Pasceri, Raffaele,Bartrum, Hannah E.,Hayes, Christopher J.,Moody, Christopher J.
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supporting information
p. 12077 - 12079
(2013/01/16)
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- Synthesis of 2-aminofurans and 2-unsubstituted furans via carbenoid-mediated [3 + 2] cycloaddition
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An efficient dual synthetic manifold for 2-aminofurans and 2-unsubstituted furans has been developed. The carbenoid-mediated [3 + 2] cycloaddition of copper carbenoids with enamines provides 2-amino-2,3-dihydrofurans which serve as common intermediates for both 2-aminofurans and 2-unsubstituted furans. The Royal Society of Chemistry 2012.
- Jiang, Yaojia,Khong, Vanessa Zhong Yue,Lourdusamy, Emmanuvel,Park, Cheol-Min
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experimental part
p. 3133 - 3135
(2012/05/04)
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