- Metal-Free Hydropyridylation of Thioester-Activated Alkenes via Electroreductive Radical Coupling
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An electrochemical hydropyridylation of thioester-activated alkenes with 4-cyanopyridines has been developed. The reactions experience a tandem electroreduction of both substrates on the cathode surface, protonation, and radical cross-coupling process, resulting in a variety of valuable pyridine variants, which contain a tertiary and even a quaternary carbon at the α-position of pyridines, in high yields. The employment of thioesters to the conjugated alkenes enables no requirement of catalyst and high temperature, representing a highly sustainable synthetic method.
- Xu, Hehuan,Liu, Jiayu,Nie, Feiyun,Zhao, Xiaowei,Jiang, Zhiyong
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p. 16204 - 16212
(2021/10/25)
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- Palladium-catalyzed thiocarbonylation of alkenes toward linear thioesters
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Thiocarbonylation of alkenes offers an ideal procedure for the synthesis of thioesters. However, thiocarbonylation of alkenes, especially styrenes, to produce valuable linear thioesters has remained a challenge. In this Letter, a general palladium-catalyz
- Ai, Han-Jun,Zhao, Fengqian,Geng, Hui-Qing,Wu, Xiao-Feng
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p. 3614 - 3619
(2021/04/07)
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- Nickel-Catalyzed Coupling of Arylzinc Halides with Thioesters
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The Pd-catalyzed Fukuyama reaction of thioesters with organozinc reagents is a mild, functional-group-tolerant method for acylation chemistry. Its Ni-catalyzed variant might be a sustainable alternative to expensive catalytic Pd sources. We investigated the reaction of S-ethyl thioesters with aryl zinc halides with hetero- and homotopic Ni precatalysts and several ligands. The results show that both homo- and heterotopic species may contribute to catalysis. The substrate scope using an operationally homogeneous defined Ni complex was established. Acyl radicals are postulated as short-lived intermediates.
- Gehrtz, Paul H.,Kathe, Prasad,Fleischer, Ivana
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supporting information
p. 8774 - 8778
(2018/06/26)
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- TMSCN/DBU-mediated facile redox transformation of α,β- unsaturated aldehydes to carboxylic acid derivatives
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Redox transformation of an α,β-unsaturated aldehyde to a carboxylic acid derivative by means of a combination of TMSCN and DBU was investigated. In addition to the wide use of the carboxylic acid derivatives provided by this reaction, temperature-dependent control of the kinetic or thermodynamic protonation pattern was found to selectively switch the stereochemistry of the acyl group in the product.
- Kaise, Hiromi,Shimokawa, Jun,Fukuyama, Tohru
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supporting information
p. 727 - 729
(2014/03/21)
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- Conjugate reduction and reductive aldol cyclization of α,β- unsaturated thioesters catalyzed by (BDP)CuH
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A conjugate reduction of α,β-unsaturated thioesters catalyzed by copper hydride using PMHS as stoichiometric reductant has been developed. 1,2-Bis(diphenylphosphino)benzene (BDP) was the most effective ligand for this reduction. Saturated thioesters could be produced in excellent yields when the substituent on the thiol is not sterically-demanding. This protocol was applied to induce the reductive aldol cyclization of keto-enethioates, which could offer β-hydroxythioesters in moderate to good yields.
- Li, Ninglin,Ou, Jun,Miesch, Michel,Chiu, Pauline
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p. 6143 - 6147
(2011/10/08)
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- 277. Structure and Chemistry of Malonylmethyl- and Succinyl-Radicals. The Search for Homolytic 1,2-Rearrangements
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Malonylmethyl radical I and its thioester analogue II were generated by standard photolytic and thermolytic methods from perester and bromo precursors.The structures of I and II were examined by ESR spectroscopy and found to exist in preferred conformations.However, no indication for their rearrangement by 1,2-shift of either an ethoxycarboxyl or (ethylthio)carbonyl group to the corresponding succinyl radicals III and IV, respectively, was found at temperatures below -40 deg C.At higher temperatures of up to 140 deg C, the search for malonylmethyl -> succinyl rearrangement was examined by thorough-product analysis of the perester decomposition.There is evidence for the rearrangement of the radical I to III by photolysis and of the radical II to IV by thermolysis at 130 deg C in chlorobenzene to only a small extent.
- Aeberhard, Urs,Keese, Reinhart,Stamm, Erich,Voegeli, Ulrich-Christian,Lau, Willy,Kochi, Jay Kazuo
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p. 2740 - 2759
(2007/10/02)
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