Silver‐Mediated C–H Difluoromethylation of Arenes

Li, Jialiang; Wan, Wen; Ma, Guobin; Chen, Yunrong; Hu, Qingyang; Kang, Kai; Jiang, Haizhen; Hao, Jian

doi:10.1002/ejoc.201600770

Cited by 30 publications

(48 citation statements)

References 56 publications

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“…2016 年, 郝健课题组等 [55] 以 AgOTf 为催化剂, KF 为助剂, 二氯乙烷为反应溶剂, TMSCF 2 COOEt 为二氟烷基化试剂, 对苯、甲苯、二甲苯及三甲苯等芳香烃及其衍生物进行芳香环 C-H 键的官能化研究. 研究发现, 增加 AgOTf、 KF 用量, 可显著提高产物的收率, 但增加 TMSCF 2 COOEt 的用量将导致产物收率大幅下降.…”

Section: 基于羟基的二氟甲基醚(R-ocf 2 H)的制备unclassified

Recent Progress on Difluoromethylation Methods

Wang¹,

Yu²,

Zhang³

et al. 2018

Chin. J. Org. Chem.

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Section: 基于羟基的二氟甲基醚(R-ocf 2 H)的制备unclassified

Recent Progress on Difluoromethylation Methods

Wang¹,

Yu²,

Zhang³

et al. 2018

Chin. J. Org. Chem.

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“…Eur.J. 2017, 23,14676 -14701 www.chemeurj.org 2017 Wiley-VCH Verlag GmbH &Co. KGaA, Weinheim rators [63] have recently accomplished aA g-mediated C Ar ÀHd ifluoromethylation of arenes.T hey employ AgOT f ,K F, and TMSCF 2 CO 2 Et in a4 :4:1 ratio, in DCE as solvent at 85 8C. The scope of the transformation is depicted in Scheme 6.…”

Section: Introductionmentioning

confidence: 99%

Difluoromethylation Reactions of Organic Compounds

Yerien

Barata‐Vallejo

Postigo

2017

Chemistry A European J

393

153

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The relevance of the -CF H moiety has attracted considerable attention from organic synthetic and medicinal chemistry communities, because this group can act as a more lipophilic isostere of the carbinol, thiol, hydroxamic acid, or amide groups. Being weakly acidic, the CF H moiety can establish hydrogen-bonding interactions to improve the binding selectivity of biologically active compounds. Therefore, the hydroxyl, amino, and thio substituents of lead structures are routinely replaced by a CF H motif in drug discovery, with great benefits in the pharmacological activity of drugs and drug candidates and agrochemicals. Consequently, the late-stage introduction of CF H is a sought-after strategy in designing bioactive compounds. Secondly, but nonetheless relevant and meaningful, is the study of synthetic pathways to introduce a CF -Y moiety (Y≠H, F) into organic substrates because compounds that contain a CF -Y functionality have also found vast applications in medicinal chemistry and in other areas, such as that of fungicides, insecticides, etc., and thus, this functionality deserves special attention. Although emphasis is made on difluoromethylation strategies to functionalize different families of organic compounds, three main methodological protocols will be presented in this review article for the late-stage introduction of a CF H or CF Y moieties into organic substrates: i) a metal-photoredox catalysis; ii) through transition metal-catalyzed thermal protocols; and iii) from transition-metal-free strategies.

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“…Advances in silver catalysis have led to new organic transformation reactions with high selectivity under mild reaction conditions. [1,2] Although silver catalysis has not been extensively studied as compared with copper and gold catalysis in the past decades, [3] distinguished reactivity modes are generally observed in silver catalysis. It is envisioned that exploration on the unique properties of silver catalysis would provide novel and efficient synthetic methodologies for organic synthesis.…”

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confidence: 99%

“…It is envisioned that exploration on the unique properties of silver catalysis would provide novel and efficient synthetic methodologies for organic synthesis. [1][2][3] Propargylic amine N-oxides, easily accessed from their corresponding propargylic amines through oxidation, [4,5] have been reported to undergo thermal Meisenheimer-type [2,3]-sigmatropic rearrangement [6] and [1,5]-hydrogen shift to give propenal in an aprotic medium or go through prototropic rearrangement to afford acrylamides and enamino aldehydes in a protic medium (Scheme 1, A). [4] However, only limited ex-amples were reported and elevated temperature was required for the reactions.…”

mentioning

confidence: 99%

“…Silver catalysis is able to activate alkynes towards nucleophilic attack through p coordination to the carbon-carbon multiple bonds. [1,2] Given the close proximity of N-oxide and alkyne moieties in the skeleton of propargylic amine N-oxides, it is envisaged that investigation of silver catalysis on the transformation of propargylic amine N-oxides would lead to novel reaction pathways that would not be observed under thermal heating conditions.…”

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confidence: 99%

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Silver‐Catalyzed Transformation of Propargylic Amine N‐Oxides to Enones and Acyloxy Ketones via Isoxazolinium Intermediates

Cui¹,

Kung²,

Ko³

et al. 2014

Adv Synth Catal

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A novel silver-catalyzed transformation of propargylic amine N-oxides with switchable product profiles has been developed. A diversity of enones with excellent E/Z ratios (up to > 20:1) were obtained when the reactions were conducted in aprotic solvents. In contrast, 3-chlorobenzoxymethyl ketones and a-(3-chloro)-benzoxy enones were obtained by using protic solvents. Mechanistic studies suggested that in situ generated isoxazolinium ions are the key intermediates involved in these novel silver-catalyzed reaction pathways. Applications on the chemoselective modification of cysteine-containing peptides in aqueous medium have also been achieved. COMMUNICATIONS Jian-Fang Cui et al. Scheme 2. A proposed reaction mechanism.

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Silver‐Mediated C–H Difluoromethylation of Arenes

Cited by 30 publications

References 56 publications

Recent Progress on Difluoromethylation Methods

Recent Progress on Difluoromethylation Methods

Difluoromethylation Reactions of Organic Compounds

Silver‐Catalyzed Transformation of Propargylic Amine N‐Oxides to Enones and Acyloxy Ketones via Isoxazolinium Intermediates

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