C–F bond functionalizations of trifluoromethyl groups via radical intermediates

Simur, Tesfaye Tebeka; Yao, Tian; Yu, You‐Jie; Zhang, Feng‐Lian; Wang, Yifeng

doi:10.1016/j.cclet.2021.08.043

Cited by 69 publications

(26 citation statements)

References 48 publications

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“…[8] Lately, several reviews of the single C(sp 3 )À F bond cleavage of trifluoromethylaromatics have been reported. [9] For example, Wang summarized recent methods used to functionalize the CÀ F bonds of CF 3 Feng Zhao was born in Hunan, China in 1988. He received his bachelor's degree in Pharmaceutical Sciences in 2011 and his doctorate in organic chemistry in 2016 from Xiangtan University under the supervision of Professor Guo-Jun Deng.…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in the Synthesis of Difluorinated Architectures from Trifluoromethyl Groups

2021

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Fluorine-containing moieties are widely used in the pharmaceutical, agrochemical, and material fields. Thus, these structures are of immense interest in the fields of organic synthesis and medicinal chemistry. Among various fluorinated groups, the difluoromethyl unit has drawn increasing attention due to its unique pharmaceutical properties. In recent years, several methods for the synthesis of difluoromethylated compounds have been rapidly developed. However, most of these methods treat aromatic compounds with excess difluoromethylating reagents, which often contain organometallic compounds, so these transformations are generally less environmentally friendly and atom-economical. In this review, we summarize the recent development of new methods for the synthesis of difluoromethyl motifs or difluoroalkenes from trifluoromethylated aromatic compounds or trifluoromethyl alkenes via single C(sp 3 )À F bond cleavage.1.

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Section: Introductionmentioning

confidence: 99%

Recent Advances in the Synthesis of Difluorinated Architectures from Trifluoromethyl Groups

2021

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“…The carboimination reaction proceeds in high yield with various N-aryl allylamines bearing electron-donating, electron-neutral, and electron-withdrawing substituents on the aromatic ring (3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18). Furthermore, we were pleased to find that a wide range of N-alkyl allylamines also proved to be effective reaction partners, and the length or bulkiness of the alkyl chain had no significantly effect on efficiency (19)(20)(21)(22)(23)(24)(25)(26)(27)(28)(29)(30)(31)(32)(33)(34)(35)(36). Notably, the reaction was well compatible with a range of functional groups (e.g., Cl, Br, ether, OBn, alkylamine, ester, C=C double bond) commonly encountered in organic synthesis.…”

Section: Resultsmentioning

confidence: 99%

“…Most of the approaches reported so far, however, feature site-selective difluorination and transformations of the pre-installed CF2-groups (11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21). The carbodefluorination of CF3 group has been recognized as one of the most ideal strategies for the synthesis of CF2-containing compounds in view of the abundant amount and low cost of CF3 sources (22)(23), despite the challenges posed by the selective cleavage of C-F bond of CF3 group, because of the high bond dissociation energy (BDE) and of over-defluorination which is often observed (24)(25)(26)(27). In the past decade, impressive advances in the controllable carbodefluorination of CF3 groups have been achieved (Fig.…”

Section: Main Textmentioning

confidence: 99%

Defluorinative Carboimination of Trifluoromethyl Ketones

Zhang

Ning

Liu

et al. 2022

Preprint

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The monofunctionalized carbodefluorination of readily accessible CF3 groups is acknowledged as an attractive approach to the preparation of partially fluorinated molecules. However, their defluorinative difunctionalization remains a challenging and unmet goal. Herein, we report an unprecedented defluorinative carboimination of trifluoromethyl ketones via a strategy of silver carbene-initiated rearrangement, in which both C–F bond and carbonyl group of the trifluoromethyl ketones were functionalized simultaneously, thus providing a straightforward synthetic method for medicinally relevant α,α-difluoroimines. The current approach involves a silver carbene-initiated intramolecular cascade process by integrating successive cleavage of C–F bond and formation of C–C and C=N bonds on a single molecule entity, which differs relevantly from the stepwise mechanism of reported carbodefluorination of CF3 groups. Mechanistic studies disclose that silver catalysis plays a critical role, particularly in the stages of C–F bond cleavage and aza-Claisen rearrangement.

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“…Therefore, we feel justified in again reviewing the topic with the same focus that characterized our earlier review. Although there have been several reviews on C-F bond cleavage recently, each review has its specific focus, such as C-F bond activation by phosphorus compounds [25], or by metalloenzymes [26], C-F functionalization of trifluoromethyl groups [27,28], catalytic enantioselective functionalization of allylic C-F bond [29], transition metal-catalyzed C(sp 2 )-F cleavage [30], and deconstructive modes of halodifluoromethyl reagents [31]. This review focuses on the C-F bond cleavage enabled by visible light photoredox catalysis since 2018, classified by the types of fluorosubstrates [32,33].…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in C-F Bond Cleavage Enabled by Visible Light Photoredox Catalysis

Zhou

2021

Molecules

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The creation of new bonds via C-F bond cleavage of readily available per- or oligofluorinated compounds has received growing interest. Using such a strategy, a myriad of valuable partially fluorinated products can be prepared, which otherwise are difficult to make by the conventional C-F bond formation methods. Visible light photoredox catalysis has been proven as an important and powerful tool for defluorinative reactions due to its mild, easy to handle, and environmentally benign characteristics. Compared to the classical C-F activation that proceeds via two-electron processes, radicals are the key intermediates using visible light photoredox catalysis, providing new modes for the cleavage of C-F bonds. In this review, a summary of the visible light-promoted C-F bond cleavage since 2018 was presented. The contents were classified by the fluorosubstrates, including polyfluorinated arenes, gem-difluoroalkenes, trifluoromethyl arenes, and trifluoromethyl alkenes. An emphasis is placed on the discussion of the mechanisms and limitations of these reactions. Finally, my personal perspective on the future development of this rapidly emerging field was provided.

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C–F bond functionalizations of trifluoromethyl groups via radical intermediates

Cited by 69 publications

References 48 publications

Recent Advances in the Synthesis of Difluorinated Architectures from Trifluoromethyl Groups

Recent Advances in the Synthesis of Difluorinated Architectures from Trifluoromethyl Groups

Defluorinative Carboimination of Trifluoromethyl Ketones

Recent Advances in C-F Bond Cleavage Enabled by Visible Light Photoredox Catalysis

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