Trifluoromethylation of Allylsilanes under Photoredox Catalysis

Mizuta, Satoshi; Engle, Keary M.; Verhoog, Stefan; Galicia‐López, Oscar; O’Duill, Miriam; Médebielle, Maurice; Wheelhouse, Katherine M. P.; Rassias, Gerasimos A.; Thompson, Amber L.; Gouverneur, Véronique

doi:10.1021/ol400184t

Cited by 126 publications

(56 citation statements)

References 20 publications

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“…A variety of reagents, such as CF 3 I, 50,[55][56][57]59,62,66,67 silver trifluoroacetate, triflyl chloride (CF 3 SO 2 Cl), 49,64 the Langlois reagent, the Togni reagent, 51,53,54,60,65 the Umemoto reagent, 48,52,58,63,65 and the Shibata reagent, 61 can act as trifluoromethyl radical (•CF 3 The excited catalyst can reduce the R f X source (oxidative quenching pathway), regeneration of the catalyst follows by means of an electron donor or else, the photoexcited catalyst could be reduced by an electron donor to a one-electron reduced species that transfers an extra electron to the R f X source (reductive quenching pathway).…”

Section: Introductionmentioning

confidence: 99%

“…: [Ru(bpy) 3 ] 2+ and facIr(ppy) 3 (bpy = 2,2´-bipyridine and ppy = 2-phenylpyridinate), can induce both oxidative 48,49,51,54,58,60,[63][64][65] and reductive 50,[55][56][57]59,62 quenching cycles, owed to the positive driving forces for electron transfer to typical perfluoroalkyl halides. 7 The competition of the two pathways precludes the elucidation of the molecular parameters of the catalysis.…”

Section: Introductionmentioning

confidence: 99%

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Photocatalytic fluoroalkylation reactions of organic compounds

2015

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Photocatalytic fluoroalkylation reactions of organic compounds

2015

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“…[8] However, the requirement of preinstalling a silyl group hampers the wide application of these methods. In addition, difunctionalization of alkenes that incorporates trifluoromethylation, such as oxytrifluoromethylation, [9] aminotrifluoromethylation, [10] orcarbotrifluoromethylation, [11,12] is another important strategy to introduce CF 3 to molecules.…”

mentioning

confidence: 99%

Copper‐Catalyzed Trifluoromethylation of Trisubstituted Allylic and Homoallylic Alcohols

Lei

Liu

Zhang

et al. 2015

Chemistry A European J

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An efficient copper-catalyzed trifluoromethylation of trisubstituted allylic and homoallylic alcohols with Togni's reagent has been developed. This strategy, accompanied by a double-bond migration, leads to various branched CF3-substituted alcohols by using readily available trisubstituted cyclic/acyclic alcohols as substrates. Moreover, for alcohols in which β-H elimination is prohibited, CF3-containing oxetanes are isolated as the sole product.

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“…The hydrogenated radical trifluoromethylation of unactivated olefins in the presence of photocatalyst was reported for the first time by the ruthenium catalyst which catalyzed in the single electron reduction of electrophilic Umemoto reagent to generate CF 3 radicals. In the same year, the group also reported the ruthenium-catalyzed radical trifluoromethylation of allyl silanes with Togni reagents (Figure 6) [31]. .…”

Section: Reduction Of Trifluoromethyl Reagents To Produce Trifluoromementioning

confidence: 98%

Research progress on trifluoromethyl-based radical reaction process

Song

2017

IOP Conf. Ser.: Earth Environ. Sci.

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Abstract. Due to the unique properties imparted by the trifluoromethyl group, such as high electron density and strong lipotropy, which effectively improve acidity, lipophilicity and metabolic stability of the molecule itself, trifluoromethyl-substituted organic compounds are becoming increasingly important as structural motifs in pharmaceuticals, agrochemicals and organic materials. In this review, we present several methods developed for the direct introduction of a trifluoromethyl group, beginning with its rich and storied history. Then the present article addresses mechanism and process in carbon-carbon bond forming reaction based on radical process which is divided into three parts according to the way of CF3 radical generation. Finally, challenges and opportunities of researches on trifluoromethylation reactions facing are prospected. IntroductionIt is well-known that organofluorine compounds are extremely rare in nature despite the relatively high abundance of fluorine in our earth's crust.The seeds of researches on fluorinated compounds were firstly planted in 1764, however, seeds didn't sprout until 1896 when Swarts successfully synthesized ethyl fluoroacetate [1]. And then the ingenious Balz-schiemann reaction moved the fluoro-organic chemistry field into a brand new stage with a better comprehension of the specific fluorine factors on the outcome of organic reactions [2].Psychotropic drugs containing F atom such as Fluphenazine was discovered in 1956 and 5-Fluorouracil in 1957 [3], brought greater hopes for cancer therapy as well as more attention on the application of fluorinated compounds. (Hetero)arenes bearing CF 3 groups constitute an indispensable part of numerous important drugs, including celecoxib, fluoxetine and fluazinam. Currently, the interest in fluoro-organic chemistry is at an all-time high.It is therefore apparent that the development of new methods for trifluoromethylation, especially in an efficient, mild and green way, is essential and necessary.It is noteworthy that new discoveries and developments of trifluoromethylation reactions are built on the researches on Trifluoromethyl reagents. Mechanisms corresponding to their regents' properties which are electrophilic, nucleophilic, or radical, can be divided into electrophilic trifluoromethylation; nucleophilic and radical. In this review, we 1) Categorize types of trifluoromethylation with presentation of the reagents in each section. 2) Introduce some recent examples of C-C bond formation based on radical way, which have appeared in the primary literature. Important earlier work in this field is also covered. 3) Focus our attention on summarizing the mechanism and propose the problems hindering the evolving chemical landscape that has engaged trifluoromethylation reactions.

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Trifluoromethylation of Allylsilanes under Photoredox Catalysis

Cited by 126 publications

References 20 publications

Photocatalytic fluoroalkylation reactions of organic compounds

Photocatalytic fluoroalkylation reactions of organic compounds

Copper‐Catalyzed Trifluoromethylation of Trisubstituted Allylic and Homoallylic Alcohols

Research progress on trifluoromethyl-based radical reaction process

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