Catalytic β C–H amination via an imidate radical relay
作者： Leah M. Stateman , Ethan A. Wappes , Kohki M. Nakafuku , Kara M. Edwards , David A. Nagib
DOI: 10.1039/C8SC05685D
关键词:
摘要: The first catalytic strategy to harness imidate radicals for C–H functionalization has been developed. This iodine-catalyzed approach enables β amination of alcohols by an imidate-mediated radical relay. In contrast our first-generation, (super)stoichiometric protocol, this method faster and more efficient reactivity. Furthermore, lower oxidant concentration affords broader functional group tolerance, including alkenes, alkynes, alcohols, carbonyls, heteroarenes. Mechanistic experiments interrogating the electronic nature key 1,5 H-atom transfer event are included, as well probes chemo-, regio-, stereo-selectivity.
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sci-hub.se 参考文章(95)
Tao Liu, Tian-Sheng Mei, Jin-Quan Yu, γ,δ,ε-C(sp3)–H Functionalization through Directed Radical H-Abstraction Journal of the American Chemical Society. ,vol. 137, pp. 5871- 5874 ,(2015) , 10.1021/JACS.5B02065
Myong Koag, Seongmin Lee, Discovery of hypoiodite-mediated aminyl radical cyclization lacking a nitrogen radical-stabilizing group: application to synthesis of an oxazaspiroketal-containing cephalostatin analog. Organic Letters. ,vol. 13, pp. 4766- 4769 ,(2011) , 10.1021/OL2017033
E. M. Chen, R. M. Keefer, L. J. Andrews, Acetyl Hypoiodite as an Aromatic Iodinating Agent Journal of the American Chemical Society. ,vol. 89, pp. 428- 430 ,(1967) , 10.1021/JA00978A046
Karl D. Collins, Frank Glorius, Intermolecular reaction screening as a tool for reaction evaluation. Accounts of Chemical Research. ,vol. 48, pp. 619- 627 ,(2015) , 10.1021/AR500434F
Tao Xiong, Qian Zhang, New amination strategies based on nitrogen-centered radical chemistry Chemical Society Reviews. ,vol. 45, pp. 3069- 3087 ,(2016) , 10.1039/C5CS00852B
Carmen Betancor, Jose I. Concepcion, Rosendo Hernandez, Jose A. Salazar, Ernesto Suarez, Intramolecular functionalization of nonactivated carbons by amidylphosphate radicals. Synthesis of 1,4-epimine compounds Journal of Organic Chemistry. ,vol. 15, pp. 4430- 4432 ,(1983) , 10.1021/JO00171A066
Marvin Parasram, Padon Chuentragool, Dhruba Sarkar, Vladimir Gevorgyan, Photoinduced Formation of Hybrid Aryl Pd-Radical Species Capable of 1,5-HAT: Selective Catalytic Oxidation of Silyl Ethers into Silyl Enol Ethers Journal of the American Chemical Society. ,vol. 138, pp. 6340- 6343 ,(2016) , 10.1021/JACS.6B01628
Edon Vitaku, David T. Smith, Jon T. Njardarson, Analysis of the Structural Diversity, Substitution Patterns, and Frequency of Nitrogen Heterocycles among U.S. FDA Approved Pharmaceuticals Journal of Medicinal Chemistry. ,vol. 57, pp. 10257- 10274 ,(2014) , 10.1021/JM501100B
Ethan A. Wappes, Stacy C. Fosu, Trevor C. Chopko, David A. Nagib, Triiodide‐Mediated δ‐Amination of Secondary C−H Bonds Angewandte Chemie. ,vol. 55, pp. 9974- 9978 ,(2016) , 10.1002/ANIE.201604704
Hongjian Lu, Kai Lang, Huiling Jiang, Lukasz Wojtas, X. Peter Zhang, Intramolecular 1,5-C(sp3)–H radical amination via Co(II)-based metalloradical catalysis for five-membered cyclic sulfamides Chemical Science. ,vol. 7, pp. 6934- 6939 ,(2016) , 10.1039/C6SC02231F