Room-temperature Formal Aza-Wacker Cyclization through Synergistic Copper/TEMPO-catalyzed Radical Relay

Published on Aug 6, 2021in ACS Catalysis12.35
· DOI :10.1021/ACSCATAL.1C02721
Dong Yang1
Estimated H-index: 1
(Sichuan University),
Jiaming Chen (Sichuan University)+ 5 AuthorsZiyuan Li11
Estimated H-index: 11
(Sichuan University)
Source
Abstract
References78
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#1Zhong ShaoH-Index: 1
#2Fang WangH-Index: 3
Last. Ziyuan Li (Sichuan University)H-Index: 11
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#1Nicholas L. Reed (UW: University of Wisconsin-Madison)H-Index: 3
#2Grace A. Lutovsky (UW: University of Wisconsin-Madison)
Last. Tehshik P. Yoon (UW: University of Wisconsin-Madison)H-Index: 50
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Oxidative heterofunctionalization reactions are among the most attractive methods for the conversion of alkenes and heteroatomic nucleophiles into complex saturated heterocycles. However, the state-of-the-art transition-metal-catalyzed methods to effect oxidative heterofunctionalizations are typically limited to unhindered olefins, and different nucleophilic partners generally require quite different reaction conditions. Herein, we show that Cu(II)-mediated radical-polar crossover allows for hig...
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#1Chong Huang (Ha Tai: Xiamen University)H-Index: 2
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The development of efficient and sustainable methods to access saturated N -heterocycles is of great importance because of the prevalence of these structures in natural products and bioactive compounds. Pd-catalyzed aza-Wacker type cyclization is a powerful method and provide access to N -heterocycles bearing an alkene moiety available for further synthetic manipulations from readily available materials. Herein we disclose a catalyst- and reagent-free formal aza-Wacker type cyclization reaction ...
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#1Liang Fu (CAS: Chinese Academy of Sciences)H-Index: 8
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The first enantioselective alkynylation of benzylic C-H bonds via copper-catalyzed radical relay has been established herein, which provides an easy access to structurally diverse benzylic alkynes ...
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#1Huayou Hu (UW: University of Wisconsin-Madison)H-Index: 1
#2Si Jie Chen (UW: University of Wisconsin-Madison)H-Index: 2
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Cross-coupling reactions enable rapid, convergent synthesis of diverse molecules and provide the foundation for modern chemical synthesis. The most widely used methods employ sp2-hybridized coupling partners, such as aryl halides or related pre-functionalized substrates. Here, we demonstrate copper-catalysed oxidative cross-coupling of benzylic C–H bonds with alcohols to afford benzyl ethers, enabled by a redox buffering strategy that maintains the activity of the copper catalyst throughout the ...
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#1Jiayuan Li (CAS: Chinese Academy of Sciences)H-Index: 1
#2Zhihan Zhang (HKUST: Hong Kong University of Science and Technology)H-Index: 9
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Methods for selective C–H bond functionalization have provided chemists with versatile and powerful toolboxes for synthesis, such as the late-stage modification of a lead compound without the need for lengthy de novo synthesis1–5. Cleavage of an sp3 C–H bond via hydrogen atom transfer (HAT) is particularly useful, given the large number of available HAT acceptors and the diversity of reaction pathways available to the resulting radical intermediate6–17. Site-selectivity, however, remains a formi...
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A TEMPO-catalysed direct amination of arene through C–H bond cleavage employing N-fluorobenzenesulfonimide (NFSI) as the amination reagent in good to excellent yields with broad arene scope in the absence of any metal, ligand or additive is reported. Unlike previous transition metal-catalysed aminations in which high reaction temperatures are usually necessary, this novel reaction at room temperature is the first example of C–H amination with NFSI that is realised via organocatalysis. The probab...
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#1Cuiying Shi (Sichuan University)H-Index: 2
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A series of small-molecule full agonists of the prostaglandin E2 type 4 (EP4) receptor have been generated and evaluated for binding affinity and cellular potency. KMN-80 and its gem-difluoro analog KMN-159 possess high selectivity relative to other prostanoid receptors. Difluoro substitution is positioned alpha to the lactam ring carbonyl and results in KMN-159’s fivefold increase in potency versus KMN-80. The two analogs exhibit electronic and conformational variations, including altered nitro...
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#1Xiangli Yi (EPFL: École Polytechnique Fédérale de Lausanne)H-Index: 1
#2Xile Hu (EPFL: École Polytechnique Fédérale de Lausanne)H-Index: 76
: In oxidative electrochemical organic synthesis, radical intermediates are often oxidized to cations on the way to final product formation. Herein, we describe an approach to transform electrochemically generated organic radical intermediates into neutral products by reaction with a metal catalyst. This approach combines electrochemical oxidation with Cu catalysis to effect formal aza-Wacker cyclization of internal alkenes. The Cu catalyst is essential for transforming secondary and primary alk...
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