- Site-Specific C(sp3)–H Aminations of Imidates and Amidines Enabled by Covalently Tethered Distonic Radical Anions
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The utilization of N-centered radicals to synthesize nitrogen-containing compounds has attracted considerable attention recently, due to their powerful reactivities and the concomitant construction of C?N bonds. However, the generation and control of N-centered radicals remain particularly challenging. We report a tethering strategy using SOMO-HOMO-converted distonic radical anions for the site-specific aminations of imidates and amidines with aid of the non-covalent interaction. This reaction features a remarkably broad substrate scope and also enables the late-stage functionalization of bioactive molecules. Furthermore, the reaction mechanism is thoroughly investigated through kinetic studies, Raman spectroscopy, electron paramagnetic resonance spectroscopy, and density functional theory calculations, revealing that the aminations likely involve direct homolytic cleavage of N?H bonds and subsequently controllable 1,5 or 1,6 hydrogen atom transfer.
- Fang, Yuanding,Fu, Kang,Shi, Lei,Zhao, Rong,Zhou, Jia
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supporting information
p. 20682 - 20690
(2020/09/07)
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- A general asymmetric synthesis of phenylglycinols
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Hydride reduction and deprotection of siloxymethyl sulfinimines 2 reliably furnished chiral phenylglycinols 1 or 10 in high overall yield and enantiomeric purity.
- Pan, Xingang,Jia, Liangbin,Liu, Xuejian,Ma, Haikuo,Yang, Wenqian,Schwarz, Jacob B.
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p. 329 - 337
(2011/05/17)
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- Formal aromatic C-H insertion for stereoselective isoquinolinone synthesis and studies on mechanistic insights into the C-C bond formation
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(Chemical Equation Presented) Formal aromatic C-H insertion of rhodium(II) carbenoid was intensively investigated to develop a new methodology and probe its mechanism. Contrasting with the previously proposed direct C-H insertion, the mechanism was revealed to be electrophilic aromatic substitution, which was supported by substituent effects on the aromatic ring and a secondary deuterium kinetic isotope effect. Various isoquinolinones were synthesized intramolecularly via six-membered ring formation with high regioand diastereoselectivity, while averting the common Buchner-type reaction. Intermolecularly, dirhodium catalyzed formal aromatic C-H insertion on electron-rich aromatics was also achieved.
- Park, Chan Pil,Nagle, Advait,Cheol, Hwan Yoon,Chen, Chiliu,Kyung, Woon Jung
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supporting information; scheme or table
p. 6231 - 6236
(2009/12/08)
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