- All-Carbon Tetrasubstituted Olefins Synthesis from Diazo Compounds and Iodonium Ylides under Blue LED Irradiation
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A route for the construction of all-carbon tetra-substituted olefins through visible-light promoted coupling of diazo compounds with iodonium ylides was developed. A wide range of all-carbon tetra-substituted olefins was obtained in moderate to good yields. The synthetic values of the current method were further approved by the synthesis of natural isolates modified alkenes and the successful transformation of final olefins into important heterocycles. (Figure presented.).
- Zhao, Yan-Rui,Li, Lei,Xu, Guo-Yong,Xuan, Jun
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supporting information
p. 506 - 511
(2021/12/08)
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- B(C6F5)3-catalyzed O-H insertion reactions of diazoalkanes with phosphinic acids
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A highly efficient base-, metal-, and oxidant-free catalytic O-H insertion reaction of diazoalkanes and phosphinic acids in the presence of B(C6F5)3has been developed. This powerful methodology provides a green approach towards the synthesis of a broad spectrum of α-phosphoryloxy carbonyl compounds with good to excellent yields (up to 99% yield). The protocol features the advantages of operational simplicity, high atom economy, practicality, easy scalability and environmental friendliness.
- Jiang, Jun,Zhang, Xinzhi,Zhang, Yangyang,Zhao, Jincheng
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p. 5772 - 5776
(2021/07/12)
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- B(C6F5)3-Catalyzed site-selective N1-alkylation of benzotriazoles with diazoalkanes
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Alkylation of benzotriazoles is synthetically challenging, often leading to mixtures of N1 and N2 alkylation. Herein, metal-free catalytic site-selective N1-alkylation of benzotriazoles with diazoalkanes is described in the presence of 10 mol% of B(C6F5)3. These reactions provide N1-alkylated benzotriazoles in good to excellent yields and this protocol is successfully adapted to gram-scale syntheses as well as a derivative with antimicrobial activity.
- Guo, Jing,Mandal, Dipendu,Stephan, Douglas W.,Wu, Yile,Zhao, Yunbo
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p. 7758 - 7761
(2021/08/13)
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- Insertion of Diazo Esters into C-F Bonds toward Diastereoselective One-Carbon Elongation of Benzylic Fluorides: Unprecedented BF3Catalysis with C-F Bond Cleavage and Re-formation
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Selective transformation of C-F bonds remains a significant goal in organic chemistry, but C-F insertion of a one-carbon-atom unit has never been established. Herein we report the BF3-catalyzed formal insertion of diazo esters as one-carbon-atom sources into C-F bonds to accomplish one-carbon elongation of benzylic fluorides. A DFT calculation study revealed that the BF3 catalyst could contribute to both C-F bond cleavage and re-formation. This elongation provided α-fluoro-α,β-diaryl esters with a high level of diastereoselectivity. Various benzylic fluorides and diazo esters were applicable. The synthetic utility of this method was demonstrated by the synthesis of a fluoro analogue of a compound that is used as a transient receptor and potential canonical channel inhibitor.
- Wang, Fei,Nishimoto, Yoshihiro,Yasuda, Makoto
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p. 20616 - 20621
(2021/11/23)
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- Visible Light-Promoted Sulfoxonium Ylides Synthesis from Aryl Diazoacetates and Sulfoxides
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A visible light-promoted reaction of donor/acceptor diazoalkanes with sulfoxides towards the synthesis of synthetically useful sulfoxonium ylides was reported. The reaction occurred under sole visible light irradiation without the need of any transition-metals or additives, affording the corresponding sulfoxonium ylides in moderate to good yields. The success of late-stage modification of natural isolates or drug candidates, scale-up reaction and transformation of sulfoxonium ylides to other useful molecules further rendered the approach valuable.
- Lu, Juan,Li, Lei,He, Xiang-Kui,Xu, Guo-Yong,Xuan, Jun
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supporting information
p. 1646 - 1650
(2021/05/28)
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- Borane Catalyzed Selective Diazo Cross-Coupling Towards Pyrazoles
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Decomposition of donor-acceptor diazo compounds leads to the formation of reactive carbene intermediates. These can undergo a wide variety of carbene transfer reactions to yield synthetically useful products. Herein, we report a selective borane catalyzed cyclization reaction from the combination of two different diazo compounds to afford N-substituted pyrazoles. The selective decomposition of the more reactive α-aryl α-diazoester and subsequent reaction with a vinyl diazoacetate produces N-alkylated pyrazoles in a regioselective manner. Catalytic amounts of tris(pentafluorophenyl)borane (10 mol%) were employed to afford the pyrazole products (36 examples) in yields from 59 to 80%. Extensive DFT studies have been undertaken to interpret the mechanism for this reaction which was found to go through two tandem catalytic cycles, both catalyzed by B(C6F5)3.
- Ariafard, Alireza,Babaahmadi, Rasool,Dasgupta, Ayan,Gierlichs, Lukas,Melen, Rebecca L.,Pahar, Sanjukta,Yates, Brian F.
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- Catalyst-free, scalable heterocyclic flow photocyclopropanation
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Industrial process development is driven by several factors, including safety, cost, robustness and environmental aspects. However, attempts to establish aryl diazo esters-which are highly valued in academic research for their reactivity as carbene precur
- Kl?pfer, Viktor,Eckl, Robert,Flo?, Johannes,Roth, Philippe M. C.,Reiser, Oliver,Barham, Joshua P.
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supporting information
p. 6366 - 6372
(2021/09/10)
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- Engineering Dirhodium Artificial Metalloenzymes for Diazo Coupling Cascade Reactions**
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Artificial metalloenzymes (ArMs) are commonly used to control the stereoselectivity of catalytic reactions, but controlling chemoselectivity remains challenging. In this study, we engineer a dirhodium ArM to catalyze diazo cross-coupling to form an alkene that, in a one-pot cascade reaction, is reduced to an alkane with high enantioselectivity (typically >99 % ee) by an alkene reductase. The numerous protein and small molecule components required for the cascade reaction had minimal effect on ArM catalysis. Directed evolution of the ArM led to improved yields and E/Z selectivities for a variety of substrates, which translated to cascade reaction yields. MD simulations of ArM variants were used to understand the structural role of the cofactor on ArM conformational dynamics. These results highlight the ability of ArMs to control both catalyst stereoselectivity and chemoselectivity to enable reactions in complex media that would otherwise lead to undesired side reactions.
- Bultman, Max J.,Huang, Rui,Lewis, Jared C.,Li, Ying,Roux, Benoit,Upp, David M.
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supporting information
p. 23672 - 23677
(2021/08/23)
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- Tropylium-Catalyzed O-H Insertion Reactions of Diazoalkanes with Carboxylic Acids
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Herein, we describe the application of a nonbenzenoid aromatic carbocation, namely tropylium, as an organic Lewis acid catalyst in O-H functionalization reactions of diazoalkanes with benzoic acids. The newly developed protocol is applicable to a wide range of diazoalkane and carboxylic acid substrates with excellent efficiency (43 examples, up to 99% yield).
- Empel, Claire,Nguyen, Thanh Vinh,Koenigs, Rene M.
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supporting information
p. 548 - 553
(2021/01/26)
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- Visible-light-promoted selective: O -alkylation of 2-pyridones with α-aryldiazoacetates
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A visible-light-promoted O-H insertion reaction between 2-pyridones and α-aryldiazoacetates has been developed. Upon visible light irradiation, the reaction proceeds smoothly under mild and catalyst-free conditions. A wide scope of 2-pyridones and α-aryldiazoacetates are well tolerated, and various O-alkylated 2-pyridones are obtained with perfect selectivity and good functional group tolerance. A photoinduced radical process is probably responsible for the excellent selectivity. This journal is
- Yang, Jingya,Wang, Ganggang,Zhou, Hongyan,Li, Zhifeng,Ma, Ben,Song, Menghui,Sun, Rongxia,Huo, Congde
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supporting information
p. 394 - 398
(2021/01/29)
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- Divergent Synthesis of Aziridine and Imidazolidine Frameworks under Blue LED Irradiation
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We develop a visible light-promoted divergent cycloaddition of α-diazo esters with hexahydro-1,3,5-triazines, leading to a series of aziridine and imidazolidine frameworks in average good yield, by simply changing the reaction media used. It is noteworthy that the reaction occurs under sole visible light irradiation without the need for exogenous photoredox catalysts. More significantly, a reasonable reaction mechanism was proposed on the basis of the control experiments and density functional theory calculation results.
- Cheng, Xiao,Cai, Bao-Gui,Mao, Hui,Lu, Juan,Li, Lei,Wang, Kun,Xuan, Jun
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supporting information
p. 4109 - 4114
(2021/05/26)
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- Oxime Ether Synthesis through O-H Functionalization of Oximes with Diazo Esters under Blue LED Irradiation
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A green and sustainable oxime ether formation method via the visible-light-promoted O-H functionalization of oximes with diazo esters is described. The reaction occurs under very mild conditions (catalyst- and additive-free) with a high yield and a high functional group tolerance. When the reaction was performed with a cyclic ether as the solvent (e.g., THF, 1,4-dioxane, tetrahydropyran, ect.), an interesting photochemical three-component reaction product was obtained in good yields.
- Li, Qian,Cai, Bao-Gui,Li, Lei,Xuan, Jun
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supporting information
p. 6951 - 6955
(2021/09/02)
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- Blue LED-Mediated N-H Insertion of Indoles into Aryldiazoesters at Room Temperature in Batch and Flow: Reaction Kinetics, Density Functional Theory, and Mechanistic Study
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Mild blue light-mediated N-H insertion of indole and its derivatives into aryldiazoesters has been reported in a batch and flow strategy to afford the corresponding N-alkylated product in moderate-to-excellent yield. Detailed high-performance liquid chromatography-based reaction kinetics measurements, control experiments, and kinetic isotope effect reveal that 3-substituted indoles with electron-withdrawing groups such as -CN and -CHO facilitated the product formation, whereas the electron-donating group retarded the process. The neutral indole performed in between them. Furthermore, Hammett plot and density functional theory-based transition-state optimization studies showed substantial correlation of the electronic nature of the substituents at the C3 position of indoles with the rate of the N-H insertion reaction. The strategy was utilized to synthesize a key intermediate for the natural product (-)-psychotrimine.
- Maiti, Debajit,Das, Ranajit,Sen, Subhabrata
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p. 2522 - 2533
(2021/02/05)
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- Blue Light-Emitting Diode-Mediated in Situ Generation of Pyridinium and Isoquinolinium Ylides from Aryl Diazoesters: Their Application in the Synthesis of Diverse Dihydroindolizine
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Blue light-emitting diode-mediated environmentally sustainable three component reactions among pyridine/isoquinoline 1/2, aryl diazoesters 3, and acrylic ester/3-alkenyl oxindoles 5/6 provide various dihydroindolizines 7 to 9 in excellent yield. The principle of the strategy is photolytic generation of nitrogen ylides from N-heteroarenes and aryl diazoesters and their subsequent [3 + 2] cycloaddition reaction with dipolarophiles. Detailed mechanistic analysis of the transformation through control experiments establishes this strategy as the foundation for the photolytic multicomponent reaction.
- Guha, Souvik,Maiti, Debajit,Prabakar, Tejas,Sar, Saibal,Sen, Subhabrata
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p. 11736 - 11747
(2021/09/02)
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- Visible light and base promoted O-H insertion/cyclization of para-quinone methides with aryl diazoacetates: An approach to 2,3-dihydrobenzofuran derivatives
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A visible light and base promoted O-H insertion/cyclization of para-quinone methides with aryl diazoacetates is developed. This one-pot two step reaction offers a mild and efficient approach for the synthesis of biologically important 2,3-dihydrobenzofuran derivatives in good yields and moderate diastereoselectivities.
- Zhou, Shuangjing,Cai, Baogui,Hu, Chuxia,Cheng, Xu,Li, Lei,Xuan, Jun
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supporting information
p. 2577 - 2581
(2021/03/22)
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- Rhodium(I)-Catalyzed Enantioselective C(sp3)—H Functionalization via Carbene-Induced Asymmetric Intermolecular C—H Insertion?
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Transition-metal-catalyzed C—H insertion of metal-carbene represents an excellent and powerful approach for C—H functionalization. However, despite remarkable advances in metal-carbene chemistry, transition metal catalysts that are capable of enantioselective intermolecular carbene C—H insertion are mainly constrained to dirhodium(II) and iridium(III)-based complexes. Herein, we disclose a new version of asymmetric carbene C—H insertion reaction with rhodium(I) catalyst. A highly enantioselective rhodium(I) complex-catalyzed C(sp3)—H functionalization of 1,4-cyclohexadienes with α-aryl-α-diazoacetates was successfully developed. By using chiral bicyclo[2.2.2]-octadiene as ligand, rhodium(I)-carbene-induced asymmetric intermolecular C—H insertion proceeds smoothly at room temperature, allowing access to a diverse variety of α-aryl-α-cyclohexadienyl acetates and gem-diaryl-containing acetates in good yields with good to excellent enantioselectivities (up to 99% ee). Furthermore, the synthetic utility of the reaction was highlighted by facile synthesis of a novel cannabinoid CB1 receptor ligand. This method may offer a new opportunity for the development of therapeutically exploitable cannabinoid receptor type ligands in medicinal chemistry.
- Liu, Bo,Xu, Ming-Hua
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supporting information
p. 1911 - 1915
(2021/05/31)
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- Blue LED Induced Manganese (I) Catalysed Direct C2?H Activation of Pyrroles with Aryl Diazoesters
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Herein, we have reported a blue LED mediated manganese pentacarbonyl bromide catalysed incorporation of carbene moieties from aryl diazoesters onto 1H-pyrroles via their selective C2?H activation. A manganese metal-carbene has been identified as the active catalyst to facilitate the reaction. Eighteen mono substituted pyrrole derivatives were isolated in good to excellent yields (67→82%) and the disubstituted products were also formed in minor quantities (5 to 8%). HPLC based kinetics study enabled optimization of the reaction. Control experiments, FT-IR, NMR and GC-MS based characterization elucidated the putative reaction mechanism. (Figure presented.).
- Sar, Saibal,Das, Ranajit,Sen, Subhabrata
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p. 3521 - 3531
(2021/06/09)
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- Photolytic amino etherification reactions of aryl diazoacetates with N-heterocycles and a stoichiometric amount of dioxane/tetrahydropyran in aqueous medium: Synthesis of 1,4-dioxepane/1,4,7-dioxazonan-6-one systems
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Herein we have reported a blue LED mediated reaction of aryl diazoacetate with a stoichiometric amount of 1,4-dioxane/tetrahydropyran (THP) and various heterocycles like indoles, pyrroles, phthalimides, thiazolidinediones and hydantoins in water. During the reaction, various aryl diazoacetates were converted to oxonium ylides by reacting with 1,4-dioxane and THP. These ylides generated in aqueous medium (under metal- and base-free conditions) were then used for the amino etherification of the aforementioned heterocycles in excellent yield. The ylides underwent a [1,2] shift to afford substituted 1,4-dioxepanes. Phthalimide products were also converted to 1,4,7-dioxazonan-6-ones. Reaction kinetics, Hammett's plot and DFT calculations (solvent phase) rationalize the ylide formation and subsequent reactions with the nucleophiles. The reaction was also demonstrated at the multigram scale. This amino etherification reaction of aryl diazoacetates in aqueous medium demonstrated a sustainable process of converting toxic 1,4-dioxane in functionalizing heterocycles. This journal is
- Das, Ranajit,Maiti, Debajit,Sen, Subhabrata
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p. 8533 - 8544
(2021/11/17)
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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 Selective C-C Bond Cleavage Strategy Promoted by Visible Light
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A new visible-light-promoted reaction between aryldiazoacetates and 1,3-diketones allows good yields and selectivities for C-C bond insertions, leading to the corresponding 1,4-dicarbonyl compounds. This transformation is straightforward and highly practical. It tolerates air and moisture and does not require the use of any metals. Mechanistic investigations support the involvement of a key cyclopropanol intermediate derived from an intramolecular rearrangement.
- Gallo, Rafael D. C.,Duarte, Marcelo,Da Silva, Amanda F.,Okada, Celso Y.,Deflon, Victor M.,Jurberg, Igor D.
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supporting information
p. 8916 - 8920
(2021/11/20)
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- Triarylborane-Catalyzed Alkenylation Reactions of Aryl Esters with Diazo Compounds
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Herein we report a facile, mild reaction protocol to form carbon–carbon bonds in the absence of transition metal catalysts. We demonstrate the metal-free alkenylation reactions of aryl esters with α-diazoesters to give highly functionalized enyne products. Catalytic amounts of tris(pentafluorophenyl)borane (10–20 mol %) are employed to afford the C=C coupled products (31 examples) in good to excellent yields (36–87 %). DFT studies were used to elucidate the mechanism for this alkenylation reaction.
- Ariafard, Alireza,Babaahmadi, Rasool,Dasgupta, Ayan,Gierlichs, Lukas,Melen, Rebecca L.,Stefkova, Katarína
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supporting information
p. 15492 - 15496
(2020/07/20)
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- Blue Light-Promoted N?H Insertion of Carbazoles, Pyrazoles and 1,2,3-Triazoles into Aryldiazoacetates
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Blue light irradiation of aryldiazoacetates leads to the formation of free carbenes, which can react with carbazoles, pyrazoles and 1,2,3-triazoles to afford the corresponding N?H inserted products. These reactions are performed under air and at room temperature, allowing the mild preparation of a variety of motifs found in biologically relevant targets. (Figure presented.).
- Stivanin, Mateus L.,Fernandes, Alessandra A. G.,da Silva, Amanda F.,Okada, Celso Y.,Jurberg, Igor D.
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p. 1106 - 1111
(2020/01/25)
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- Room Temperature Coupling of Aryldiazoacetates with Boronic Acids Enhanced by Blue Light Irradiation
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A visible-light-promoted photochemical protocol is reported for the coupling of aryldiazoacetates with boronic acids. This photochemical reaction shows great enhancement compared to the same protocol performed in the absence of light. Except for a few cases, the room temperature coupling in the dark (thermal process) generally does not work. When it does, it is likely to also involve free carbenes as key intermediates. Alternatively, photochemical reactions show a broad scope, can be performed under air and tolerate a wide variety of functional groups. Reaction-evolution monitoring, DFT calculations and control experiments have been used to evaluate the main aspects of this intricate mechanistic scenario. Biologically active molecules Adiphenine, Benactyzine and Aprophen have been prepared as examples of synthetic applications.
- da Silva, Amanda F.,Afonso, Marco A. S.,Cormanich, Rodrigo A.,Jurberg, Igor D.
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p. 5648 - 5653
(2020/04/22)
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- Pd-Catalyzed Decarboxylative Olefination: Stereoselective Synthesis of Polysubstituted Butadienes and Macrocyclic P-glycoprotein Inhibitors
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The efficient and stereoselective synthesis of polysubstituted butadienes, especially the multifunctional butadienes, represents a great challenge in organic synthesis. Herein, we wish to report a distinctive Pd(0) carbene-initiated decarboxylative olefination approach that enables the direct coupling of diazo esters with vinylethylene carbonates (VECs), vinyl oxazolidinones, or vinyl benzoxazinones to afford alcohol-, amine-, or aniline-containing 1,3-dienes in moderate to high yields and with excellent stereoselectivity. This protocol features operational simplicity, mild reaction conditions, a broad substrate scope, and gram-scalability. Notably, a structurally unique allylic Pd(II) intermediate was isolated and characterized. DFT calculation and control experiments demonstrated that a rare Pd(0) carbene intermediate could be involved in this reaction. Moreover, the polysubstituted butadienes as novel building blocks were unprecedentedly assembled into macrocycles, which efficiently inhibited the P-glycoprotein and dramatically reversed multidrug resistance in cancer cells by 190-fold.
- Chen, Xiangyang,Hao, Jiping,Houk, K. N.,Li, Yingzi,Lou, Liguang,Quan, Haitian,Song, Bichao,Wang, Lu,Xia, Yuanzhi,Xie, Peipei,Xu, Zhongliang,Yang, Weibo
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p. 9982 - 9992
(2020/06/27)
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- Borane-Catalyzed Stereoselective C–H Insertion, Cyclopropanation, and Ring-Opening Reactions
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Lewis acidic boranes have been shown to be effective metal-free catalysts for highly selective reactions of donor-acceptor diazo compounds to a range of substrates. The reactions of α-aryl α-diazoesters with nitrogen heterocycles indole or pyrrole selectively generate C3 and C2 C–H insertion products, respectively, in good to excellent yields even when using unprotected indoles. Alternatively, benzofuran, indene, and alkene substrates give exclusively cyclopropanated products with α-aryl α-diazoesters, whereas the reactions with furans lead to ring-opening. Comprehensive theoretical calculations have been used to explain the differing reactivities and high selectivities of these reactions. Overall, this work demonstrates the selective metal-free catalytic reactions of α-aryl α-diazoesters with (hetero)cycles and alkenes. This simple, mild reaction protocol represents an alternative to the commonly used precious metal systems and may provide future applications in the generation of biologically active compounds. Efficient and facile routes to heterocyclic compounds are highly desirable because of their remarkable biological importance and applications in drugs approved by the Food and Drug Administration. Current synthetic routes frequently use precious metal-catalyzed reactions. The problems associated with the limited resources of precious metals as well as their toxicities can be avoided through metal-free approaches. Our investigations on the reactivities of diazoesters toward the (hetero)arenes reveal that by using Lewis acidic triarylboranes as a catalyst, we can selectively effect C–H insertion, cyclopropanation, or ring-opening in good to excellent yields. Main group, or metal-free, catalysis has become a burgeoning field; yet, this flourishing field is still in its nascent stage. The work described herein represents a step toward improving the applicability of main group catalysis by employing metal-free approaches in the functionalization of organic compounds. This work demonstrates the highly selective metal-free catalytic reactions of α-aryl α-diazoesters with a range of (hetero)cycles and olefins using Lewis acidic boranes. The simple, mild reaction protocol employed represents an alternative to the commonly used precious metal systems and may provide future applications in the generation of biologically active compounds.
- Dasgupta, Ayan,Babaahmadi, Rasool,Slater, Ben,Yates, Brian F.,Ariafard, Alireza,Melen, Rebecca L.
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supporting information
p. 2364 - 2381
(2020/08/14)
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- Photochemical Doyle-Kirmse Reaction: A Route to Allenes
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This Letter describes the metal-free, blue-light-induced [2,3]-sigmatropic rearrangement of sulfonium ylides generated from donor/acceptor diazoalkanes and propargyl sulfides. The reaction furnishes highly functionalized allenes from a broad range of starting materials in decent yield. Mechanistic experiments supported by the literature data suggest singlet carbenes as intermediates in this reaction.
- Or?owska, Katarzyna,Rybicka-Jasińska, Katarzyna,Krajewski, Piotr,Gryko, Dorota
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supporting information
p. 1018 - 1021
(2020/01/31)
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- Catalytic O-H bond insertion reactions using surface modified sewage sludge as a catalyst
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Developing a greener, sustainable catalyst is a very important but challenging task in organic synthesis. Herein, for the first time, we choose more economical and greener surface modified sewage sludge-derived carbonaceous materials (SW) treated by perch
- Baell, Jonathan B.,He, Yide,Huang, Fei,Huang, He,Xu, Yao,Yi, Xiangyan,Yu, Yang,Zhang, Zhipeng
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supporting information
p. 1594 - 1604
(2020/03/26)
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- Catalytic C-C coupling of diazo compounds with arylboronic acids: Using surface modified sewage sludge as catalyst
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A green, mild and efficient synthesis of diarylmethines using sewage sludge-derived carbonaceous materials (SW) by perchloric acid catalyzed coupling reactions between diazo compounds and arylboronic acids was developed. The reaction shows a high level of functional tolerance and a broad substrate scope. Furthermore, the highly selective 1,2-alkyl shift products were furnished through the sterically demanding R4, R5 migration of diazo compounds (3-diazochromanone). The structures of 1,2-shift products have been further confirmed by single-crystal X-ray analysis. Significantly, the synthesis of the core structures of darifenacin (a clinical drug for overactive bladder syndrome, OAB) and diclofensine (a stimulant drug showing antidepressant and monoamine reuptake inhibitor activity) further demonstrated the efficacy and synthetic potential of this method. This journal is
- Huang, Fei,Huang, He,Hughes, Timothy,Xie, Yuxing,Xu, Jun,Yu, Yang,Zhang, Zhipeng
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supporting information
p. 4165 - 4173
(2020/07/14)
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- Copper-catalyzed carbene insertion and ester migration for the synthesis of polysubstituted pyrroles
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Copper-catalyzed carbene insertion/ester migration/cyclization of enaminones and α-diazo compounds occurred efficiently to afford 2-ester polysubstituted pyrroles under mild conditions in moderate-to-good yields. Substituent functionality was well tolerated and13C-labelled experiments demonstrated 1,2-ester migration during the reaction.
- Li, Mingrui,Sun, Yiming,Xie, Yuxing,Yu, Yang,Huang, Fei,Huang, He
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supporting information
p. 11050 - 11053
(2020/10/05)
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- Diastereoselective Trapping of Transient Carboxylic Oxonium Ylides with α,β-Unsaturated 2-Acyl Imidazoles
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By developing a diastereoselective reaction of cyclopropene carboxylic acids with α,β-unsaturated 2-acyl imidazoles, we reported here a Michael-type trapping of transient carboxylic oxonium ylides. This transformation provides a direct approach for the construction of valuable γ-butenolide derivatives in good yields (60–99%) with high diastereoselectivities (up to >95:5 dr) under mild reaction conditions. (Figure presented.).
- Zhang, Mengchu,Zhang, Tianyuan,Zhang, Dan,Hu, Wenhao
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supporting information
p. 4662 - 4667
(2020/09/23)
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- Catalytic Enantio- And Diastereoselective Cyclopropanation of 2-Azadienes for the Synthesis of Aminocyclopropanes Bearing Quaternary Carbon Stereogenic Centers
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We report the catalytic enantio- and diastereoselective preparation of aminocyclopropanes by the cyclopropanation of terminal and (Z)-internal 2-azadienes with donor/acceptor carbenes derived from α-diazoesters. The resulting cyclopropanes bear quaternary carbon stereogenic centers vicinal to the amino-substituted carbon and are formed as a single diastereomer in up to 99:1 er and 97% yield with 0.5 mol % of Rh2(DOSP)4 and only 1.5 equiv of the diazo reagent. Transformations with internal azadienes afford cyclopropanes with three contiguous stereogenic centers.
- Shao, Xinxin,Malcolmson, Steven J.
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supporting information
p. 7380 - 7385
(2019/10/02)
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- Glycosylation Enabled by Successive Rhodium(II) and Br?nsted Acid Catalysis
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Herein, we reported on a highly efficient glycosylation reaction comprising two chronological meticulously designed catalytic cycles: (1) rhodium-catalyzed formation of sulfonium ylide and (2) Br?nsted acid-catalyzed formation of sulfonium ion. This protocol highlighted an effective and robust tactic to prepare a glycosyl sulfonium ion from a glycosyl sulfonium ylide precursor amenable for glycosylation.
- Meng, Lingkui,Wu, Peng,Fang, Jing,Xiao, Ying,Xiao, Xiong,Tu, Guangsheng,Ma, Xiang,Teng, Shuang,Zeng, Jing,Wan, Qian
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supporting information
p. 11775 - 11780
(2019/08/20)
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- Convenient Approach to 2-Substituted (Thio)morpholin-3-ones from α-Diazoacetates via X-H Carbene Insertion – Lactamization Sequence
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Stepwise coupling of N-Boc-protected β-aminoethanols or β-mercaptoethylamines with various α-diazoacetates provides a new, unified approach to constructing (thio)morpholin-3-ones. The process involves a Rh2(esp)2-catalyzed X-H insert
- Solovyov, Igor,Dar'in, Dmitry,Krasavin, Mikhail
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p. 7432 - 7438
(2019/11/28)
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- Photochemical, Metal-Free Sigmatropic Rearrangement Reactions of Sulfur Ylides
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Sigmatropic rearrangement reactions constitute one of the most fundamental reactions of carbenes. While state-of-the-art synthetic methods require the use of expensive precious metal catalysts, the application of visible light for the photolysis of α-aryldiazoacetates is much less investigated and provides an operationally simple entry to carbenes under mild reaction conditions. Herein, we report on blue-light induced sigmatropic rearrangement reactions of sulfur compounds with α-aryldiazoacetates. This process, depending on the substitution pattern of the sulfide, opens up formal insertion reactions of carbenes into S?N, S?C, or C?H bonds.
- Yang, Zhen,Guo, Yujing,Koenigs, Rene M.
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supporting information
p. 6703 - 6706
(2019/05/10)
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- Catalytic asymmetric synthesis of 2,5-dihydrofurans using synergistic bifunctional Ag catalysis
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We report a bifunctional Ag catalyst promoted intramolecular capture of oxonium ylides with alkynes for the enantioselective synthesis of 2,5-dihydrofurans. This represents unprecedented synergistic catalysis of a bifunctional Ag catalyst. Mechanistic studies revealed that [(R)-3,5-DM-BINAP](AgSbF6)2 (9) is likely to be the active catalytic species and that the reaction involves second order kinetics with respect to 9, suggesting that two molecules of 9 are involved in the intramolecular trapping of a Ag-associated oxonium ylide with a Ag-activated alkyne. Based on our mechanistic hypothesis, we further optimized the reaction, rendering a facile approach to 2,5-dihydrofurans in good to excellent yields in a highly chemo- and enantioselective fashion.
- Shi, Taoda,Teng, Shenghan,Gopi Krishna Reddy, Alavala,Guo, Xin,Zhang, Yueteng,Moore, Kohlson T.,Buckley, Thomas,Mason, Damian J.,Wang, Wei,Chapman, Eli,Hu, Wenhao
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supporting information
p. 8737 - 8744
(2019/10/16)
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- Norcaradiene Synthesis via Visible-Light-Mediated Cyclopropanation Reactions of Arenes
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Cyclopropanation reactions of carbenes with arenes provide a straightforward pathway to norcaradienes or cycloheptatrienes. This reaction normally requires harsh reaction conditions or transition-metal catalysts. In this report, we describe the metal-free visible-light photolysis of aryl diazoacetates in aromatic solvents, which provides access to the norcaradiene ring system in a highly regio- and stereoselective manner. The mild reaction conditions of this approach also allow chemoselective cyclopropanation of substituted arenes without competing C-H functionalization reactions.
- Guo, Yujing,Nguyen, Thanh Vinh,Koenigs, Rene M.
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supporting information
p. 8814 - 8818
(2019/11/03)
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- Pd-Catalyzed Three-Component Domino Reaction of Vinyl Benzoxazinanones for Regioselective and Stereoselective Synthesis of Allylic Sulfone-Containing Amino Acid Derivatives
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A Pd-catalyzed, highly regioselective and stereoselective three-component domino allylic substitution/N-H carbene insertion reaction under mild conditions is described. This reaction demonstrates a wide substrate scope and satisfactory functional group tolerance, providing a broad range of allylic sulfone-containing amino acid derivatives. Moreover, DBU mediates highly diastereoselective cross-dehydrogenative coupling annulation of allylic sulfones without using peroxides or any metal oxidants. This developed protocol affords 7-membered ring heterocyclic compounds incorporating both sulfone-containing amino acid esters and one quaternary carbon center. Mechanistic studies indicate that an unusual umpolung of glycine occurred in this annulation.
- Hao, Jiping,Xu, Yi,Xu, Zhongliang,Zhang, Zhiqiang,Yang, Weibo
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p. 7888 - 7892
(2019/01/04)
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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 0038-0040
(2018/11/22)
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- Rh(ii)/phosphine-cocatalyzed synthesis of dithioketal derivatives from diazo compounds through simultaneous construction of two different C-S bonds
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Rhodium(ii)/phosphine-cocatalyzed bis-sulfuration of α-diazocarbonyl compounds using thiosulfonates as the sulfenylating agent, which provided two sulfur-containing moieties, was developed via simultaneous inter- and intra-molecular C-S bond formation. This novel protocol provides a rapid synthetic route to dithioketal derivatives in moderate to good yields in an atom-economic process. The transformation is proposed to proceed through phosphine ylide formation followed by S(O2)-S bond cleavage and rearrangement.
- Rao, Changqing,Mai, Shaoyu,Song, Qiuling
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supporting information
p. 5964 - 5967
(2018/06/18)
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- Au Nanoparticle-Catalyzed Insertion of Carbenes from α-Diazocarbonyl Compounds into Hydrosilanes
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Supported Au nanoparticles on TiO2 catalyze the insertion of carbenes from α-diazocabonyl compounds into hydrosilanes. It is proposed that the transformation involves two modes of catalytic activation: formation of nucleophilic Au carbenes on the surface of nanoparticle via expulsion of N2 and activation of the Si-H bond of hydrosilane on Au nanoparticle, followed by coupling of the chemisorbed species. No external ligands or additives are required, while the process is purely heterogeneous, thus allowing the recycling and reuse of the catalyst.
- Kidonakis, Marios,Stratakis, Manolis
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supporting information
p. 4086 - 4089
(2018/07/15)
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- Copper-Catalyzed Carbenoid Insertion Reactions of α-Diazoesters and α-Diazoketones into Si-H and S-H Bonds
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An efficient copper-catalyzed carbenoid insertion reaction of α-diazo carbonyl compounds into Si-H and S-H bonds was developed. A wide range of α-silylesters and α-thioesters was obtained in high yields (up to 98%) from α-diazoesters using 5 mol% of a simple copper(I) salt as catalyst. Using 0.05 mol% of the same catalyst, α-diazoketones led to α-silylketones in low to good yields (up to 70%).
- Keipour, Hoda,Jalba, Angela,Delage-Laurin, Léo,Ollevier, Thierry
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p. 3000 - 3010
(2017/03/23)
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- Iron-Catalyzed Carbene Insertion Reactions of α-Diazoesters into Si-H Bonds
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An efficient iron-catalyzed carbene insertion reaction of α-diazo carbonyl compounds into the Si-H bond was developed. A wide range of α-silylesters was obtained in high yields (up to 99%) from α-diazoesters using a simple iron(II) salt as catalyst.
- Keipour, Hoda,Ollevier, Thierry
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supporting information
p. 5736 - 5739
(2017/11/10)
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- Rhodium(II)/Chiral Phosphoric Acid-Cocatalyzed Enantioselective O–H Bond Insertion of α-Diazo Esters
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A rhodium(II)/chiral phosphoric acid system has been developed for the asymmetric catalytic insertion of α-diazo esters into the O–H bond of carboxylic acids to generate an array of synthetically useful α-hydroxy ester derivatives in good ee (up to 95% ee). Furthermore, the substrate scope could be successfully extended to a range of phenols and alcohols with high yield (up to 92%) and excellent enantioselectivity (up to 97%) under mild reaction conditions. Additionally, a density functional theory (DFT) study was performed to elucidate the reaction mechanism. (Figure presented.).
- Zhang, Yiliang,Yao, Yuan,He, Li,Liu, Yang,Shi, Lei
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supporting information
p. 2754 - 2761
(2017/08/23)
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- The Rh(II)-catalyzed formal N-S bond insertion reaction of aryldiazoacetates into: N -phenyl-sulfenyl phthalimide
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The Rh(ii)-catalyzed sulfur ylide [1,2]-rearrangement of carbenoids generated from aryldiazoacetates has been realized via N-S bond insertion, generating tertiary sulfides in moderate to excellent yields. This demonstrates the first use of the sulfur ylide [1,2]-rearrangement undergoing N-S bond insertion. This protocol could proceed smoothly with high regioselectivity, low catalyst loading (0.1 mol% Rh2(OAc)4), gram-scale reaction and broad substrate scope. And the product could be converted into glycine derivatives through simple procedures.
- Song, Zhuang,Wu, Yizhou,Xin, Tao,Jin, Chao,Wen, Xiaoan,Sun, Hongbin,Xu, Qing-Long
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supporting information
p. 6079 - 6082
(2016/05/19)
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- Catalyst-Free S–S Bond Insertion Reaction of a Donor/Acceptor-Free Carbene by a Radical Process: A Combined Experimental and Computational Study
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Herein, a donor/acceptor-free carbene insertion reaction of an S–S bond through a radical process is presented. This catalyst-free reaction was thermally induced and provided the dithioketal products in moderate to high yields. A mechanism involving radical intermediates was proposed according to the computational study, and these intermediates were verified experimentally and intercepted for the first time by using a cross-coupling reaction.
- Zheng, Yang,Bian, Rongjian,Zhang, Xiaolu,Yao, Ruwei,Qiu, Lihua,Bao, Xiaoguang,Xu, Xinfang
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supporting information
p. 3872 - 3877
(2016/08/16)
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- Copper-Catalyzed Regiospecific and 1,2-Regioselective Cyclopropanation of (1 Z)-1-Amino- and (1 Z)-1-Oxy-1,3-butadienyl Derivatives
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The copper-catalyzed regiospecific and 1,2-regioselective cyclopropanation of (1Z)-1-amino- and (1Z)-1-oxy-1,3-butadienyl derivatives, which could be prepared by Z-stereoselective 1,4-elimination with α-aryl diazoesters was successfully demonstrated. This successful regiospecific protocol enabled the preparation of the corresponding 1-amino- and 1-oxy-2-vinylcyclopropane derivatives as almost single stereoisomers.
- Tayama, Eiji,Saito, Shun
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p. 1880 - 1884
(2015/08/06)
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- Cobalt(III)-Catalyzed Directed C-H Coupling with Diazo Compounds: Straightforward Access towards Extended π-Systems
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The first highly efficient and scalable cobalt-catalyzed directed C-H functionalization with carbene precursors is presented. This methodology provides a modular route towards a new class of conjugated polycyclic hydrocarbons with tunable emission wavelengths both in solution and in the solid state.
- Zhao, Dongbing,Kim, Ju Hyun,Stegemann, Linda,Strassert, Cristian A.,Glorius, Frank
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supporting information
p. 4508 - 4511
(2015/04/14)
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- Pd(ii)-catalyzed formal [4+1] cycloaddition reactions of diazoacetates and aryl propargyl alcohols to form 2,5-dihydrofurans
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A Pd(ii)-catalyzed formal [4+1] cycloaddition of aryl diazoacetates and aryl propargyl alcohols is reported to afford 2,5-dihydrofuran derivatives as the dominant product over other traditional ones. The auto-tandem catalytic process is proposed to occur via Pd(ii)-catalyzed intermolecular oxonium ylide formation and subsequent intramolecular trapping of the ylide with Pd(ii)-activated alkynes.
- Shi, Taoda,Guo, Xin,Teng, Shenghan,Hu, Wenhao
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supporting information
p. 15204 - 15207
(2015/10/12)
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- Copper(II)-acid catalyzed cyclopropanation of 1,3-dienamides by electrophilic activation of α-aryl diazoesters
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Copper(II)-acid catalyzed cyclopropanation of electron-rich alkenes, such as 1,3-dienamides, with α-aryl diazoesters are described. The reaction could be performed without rare metal catalysts, excess substrate, or the need for the slow addition of the diazoesters.
- Tayama, Eiji,Horikawa, Kouki,Iwamoto, Hajime,Hasegawa, Eietsu
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supporting information
p. 3041 - 3044
(2014/05/20)
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- Efficient synthesis of chiral cyclic acetals by metal and Bronsted acid co-catalyzed enantioselective four-component cascade reactions
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Four-component Mannich reactions subsequently followed by an intramolecular oxo-Michael addition were developed to efficiently produce chiral cyclic acetals with high diastereoselectivity and enantioselectivity. The Royal Society of Chemistry.
- Qiu, Lin,Guo, Xin,Ma, Chaoqun,Qiu, Huang,Liu, Shunying,Yang, Liping,Hu, Wenhao
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supporting information
p. 2196 - 2198
(2014/02/14)
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