Transition‐Metal‐Free Visible Light‐Induced Imino‐trifluoromethylation of Unsaturated Oxime Esters: A Facile Access to CF<sub>3</sub>‐Tethered Pyrrolines

Chen, Bin; He, Han; Xu, Jiawei; Guo, Kang; Xu, Ning; Chen, Kang; Zhu, Yingguang

doi:10.1002/ajoc.202100429

Cited by 7 publications

(11 citation statements)

References 123 publications

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“…Chen, Zhu and coworkers reported an intramolecular amino‐trifluoromethylation of unsaturated oxime esters with Langlois reagent under photocatalytic conditions, using rhodamine B as an organophotocatalyst (Scheme 111). [128] This reaction was postulated to proceed via the generation of a nitrogen‐centered radical through the reduction of the oxime ester with the reduced form of the catalyst followed by pyrroline skeleton‐forming radical cyclization. The resulting radical reacts with the CF 3 radical generated by the oxidation of Langlois reagent with the excited photocatalyst.…”

Section: Amino‐trifluoromethylationmentioning

confidence: 99%

“…Pyrroline-forming amino-trifluoromethylation of alkene-bearing oxime esters. [128] Liu and coworkers achieved asymmetric aminotrifluoromethylation using a copper-CPA dual-catalytic system (Scheme 101) and the readily available trifluoromethanesulfonyl chloride (Scheme 112). [129] The key for the success of this transformation was the use of Ag 2 CO 3 to scavenge the in situ generated HCl and thus prevent the undesired hydroamination.…”

Section: Intramolecular Amino-trifluoromethylationmentioning

confidence: 99%

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Evolution and Future of Hetero‐ and Hydro‐Trifluoromethylations of Unsaturated C−C Bonds

et al. 2023

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The difunctionalizative trifluoromethylation of unsaturated CÀ C bonds is a highly useful and efficient method for the synthesis of trifluoromethyl compounds with attractive architectures from simple feedstocks, allowing the introduction of the CF 3 group along with a wide variety of substituents either inter-or intramolecularly. Given that trifluoromethyl molecules are increasingly used as promising bioactive species in the design of new drugs and agrochemicals, difunctionalizative trifluoromethylation has been extensively studied during the last decade. This review focuses on reactions proceeding via the simultaneous formation of CÀ heteroatom (O, N, S, Se, B) and CÀ H bonds, as these reactions provide useful CF 3 group-containing building blocks. To identify the trends and prospects of the evolution of this methodology, we systematically describe the variants of these types of reactions and provide a more general view of reaction conditions, modes, and mechanisms. The presented comprehensive survey enables the categorization of reactions into those that are synthetically mature and those with room for further development. 1.Shintaro Kawamura completed his Ph.D. at Kyoto University in 2013 under the supervision of Prof. Masaharu Nakamura. Since 2012, he has worked in Prof. Mikiko Sodeoka's group at RIKEN. He was promoted from a postdoctoral researcher to a Research Scientist (2017) and then to a Senior Research Scientist (2021) at RIK-EN. Dr. Kawamura's research interests include fluoroalkylation reactions based on the precise reactivity control of radical species. Pablo Barrio completed his Ph.D. at the University of Oviedo in 2007 under the supervision of Prof. Barluenga. After a postdoctoral role in the group of Prof. Carreira at ETH Zurich, he joined the group of Prof. Fustero in 2009 as a Juan de la Cierva Fellow, working for several years in the field of organofluorine chemistry. In 2018, he moved to Oviedo as a Ramón y Cajal Fellow, joining the Selective Organic Synthesis (SOS) group. Dr. Barrio's research interests include gold catalysis. Santos Fustero studied Chemistry at the University of Zaragoza, where he obtained his B.S. and Ph.D. under the supervision of Prof. Barluenga and Prof. Gotor. He spent two years as a postdoctoral research associate at Prof. Lehmkuhl's laboratory at Max-Planck-Institut für Kohlenforschung in Mülheim an der Ruhr, Germany. In 1983, he became Associate Professor at the University of Oviedo, Spain, and was promoted to Full Professor at the University of Valencia in 1990. In 2005, he became a research group leader at Centro de Investigación Príncipe Felipe in Valencia. Prof. Fustero's research interests include organofluorine and medicinal chemistry, organocatalysis, heterocyclic chemistry, and new reaction methodologies. Jorge Escorihuela received his Ph.D. in Chemistry at Universitat Jaume I (Castellon, Spain) in 2009. After a postdoctoral stage at Universitat Politècnica de València (UPV), he worked at Wageningen University and Research (the Netherlands) with Prof. Zuilho...

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Section: Amino‐trifluoromethylationmentioning

confidence: 99%

Section: Intramolecular Amino-trifluoromethylationmentioning

confidence: 99%

Evolution and Future of Hetero‐ and Hydro‐Trifluoromethylations of Unsaturated C−C Bonds

et al. 2023

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“…By ⋅CF 3 addition and cyclization of variously substituted isonitriles, a diverse group of CF 3 ‐containing phenanthridines can be formed. Chen, Zhu, and coworkers reported the synthesis of CF 3 ‐containing pyrrolines [153] . This work utilizes 22 and organocatalyst Rhodamine B to provide the iminotrifluoromethylation of unsaturated oxime esters.…”

Section: Trifluoromethylation (Cf3)mentioning

confidence: 99%

“…Chen, Zhu, and coworkers reported the synthesis of CF 3containing pyrrolines. [153] This work utilizes 22 and organocatalyst Rhodamine B to provide the iminotrifluoromethylation of unsaturated oxime esters. The protocol relies on the generation of an iminyl radical (via reductive NÀ O bond cleavage), and radical-radical coupling to form the trifluoromethyl-tethered products.…”

Section: Trifluoromethylation Cascade Reactionsmentioning

confidence: 99%

Recent Advances in Visible Light‐Mediated Radical Fluoro‐alkylation, ‐alkoxylation, ‐alkylthiolation, ‐alkylselenolation, and ‐alkylamination

Lin

Coe

Krishnamurti

et al. 2023

The Chemical Record

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In the last few years, many reagents and protocols have been developed to allow for the efficient fluorofunctionalization of a diverse set of scaffolds ranging from alkanes, alkenes, alkynes, and (hetero)arenes. The concomitant rise of organofluorine chemistry and visible light‐mediated synthesis have synergistically expanded the fields and have mutually benefitted from developments in both fields. In this context, visible light driven formations of radicals containing fluorine have been a major focus for the discovery of new bioactive compounds. This review details the recent advances and progress made in visible light‐mediated fluoroalkylation and heteroatom centered radical generation.

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“…The resulting cyclic radical must then be oxidized to enable catalyst turnover (Scheme a). This requirement constrains the type of reagents that can be employed to functionalize the intermediate adduct. , …”

Section: Introductionmentioning

confidence: 99%

Microwave- and Thermally Promoted Iminyl Radical Cyclizations: A Versatile Method for the Synthesis of Functionalized Pyrrolines

et al. 2022

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A detailed study of iminyl radical cyclizations of O-aryloximes tethered to alkenes is reported. The reactions can be triggered by either microwave irradiation or conventional heating in an oil bath. A variety of radical traps can be employed, enabling C–C, C–N, C–O, C–S, or C–X bond formation and producing a diverse array of functionalized pyrrolines. Substrates containing an allylic sulfide furnish terminal alkenes by a tandem cyclization–thiyl radical β-elimination pathway. Cyclizations of hydroxylated substrates exhibit moderate diastereoselectivity that in some cases can partially be attributed to intramolecular hydrogen bonding. Computational studies suggested a possible role for thermodynamics in controlling the stereochemistry of cyclizations. The reaction temperature can be lowered from 120 to 100 °C by employing O-(p-tert-butylphenyl)oximes instead of O-phenyloximes as substrates, and these second-generation iminyl radical precursors can be used in a one-pot oxime ether formation–cyclization that is promoted by conventional heating. The functionalized pyrrolines obtained from these reactions can be conveniently transformed in several different ways.

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Transition‐Metal‐Free Visible Light‐Induced Imino‐trifluoromethylation of Unsaturated Oxime Esters: A Facile Access to CF₃‐Tethered Pyrrolines

Cited by 7 publications

References 123 publications

Evolution and Future of Hetero‐ and Hydro‐Trifluoromethylations of Unsaturated C−C Bonds

Evolution and Future of Hetero‐ and Hydro‐Trifluoromethylations of Unsaturated C−C Bonds

Recent Advances in Visible Light‐Mediated Radical Fluoro‐alkylation, ‐alkoxylation, ‐alkylthiolation, ‐alkylselenolation, and ‐alkylamination

Microwave- and Thermally Promoted Iminyl Radical Cyclizations: A Versatile Method for the Synthesis of Functionalized Pyrrolines

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Transition‐Metal‐Free Visible Light‐Induced Imino‐trifluoromethylation of Unsaturated Oxime Esters: A Facile Access to CF3‐Tethered Pyrrolines

Cited by 7 publications

References 123 publications

Evolution and Future of Hetero‐ and Hydro‐Trifluoromethylations of Unsaturated C−C Bonds

Evolution and Future of Hetero‐ and Hydro‐Trifluoromethylations of Unsaturated C−C Bonds

Recent Advances in Visible Light‐Mediated Radical Fluoro‐alkylation, ‐alkoxylation, ‐alkylthiolation, ‐alkylselenolation, and ‐alkylamination

Microwave- and Thermally Promoted Iminyl Radical Cyclizations: A Versatile Method for the Synthesis of Functionalized Pyrrolines

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Transition‐Metal‐Free Visible Light‐Induced Imino‐trifluoromethylation of Unsaturated Oxime Esters: A Facile Access to CF₃‐Tethered Pyrrolines