Lewis Acid‐Mediated Cyanation of Phenols Using N‐Cyano‐N‐phenyl‐p‐toluenesulfonamide

Zhang, Wu; Li, Tao; Wang, Qingli; Zhao, Wanxiang

doi:10.1002/adsc.201900813

Cited by 10 publications

(6 citation statements)

References 46 publications

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“…In these reactions, the choice of cyano sources was significant for obtaining high efficiency. Electrophilic cyanating reagents, such as BrCN, [19a] N ‐cyano‐ N ‐phenyl‐ p ‐toluenesulfonamide (NCTS), [19e,20b] could smoothly react with electron‐rich arenes. However, these reagents had some disadvantages such as high toxicity of BrCN or high cost of NCTS.…”

Section: Methodsmentioning

confidence: 99%

Electrochemical Oxidative C−H Cyanation of Quinoxalin‐2(1H)‐ones with TMSCN

Zhan

Tong

et al. 2021

Eur J Org Chem

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Both quinoxalin-2(1H)-ones and nitriles are valuable organic compounds, and it is an interesting task to introduce cyano into quinoxalin-2(1H)-ones. Herein a regioselective CÀ H cyanation of quinoxalin-2(1H)-ones was developed with a nucleophilic cyano source TMSCN under electrochemical oxidative conditions. This process allowed the synthesis of C3 cyanated quinoxalin-2(1H)ones in moderate to excellent yields in the absence of transition-metal catalysts and organic hydroperoxides.Quinoxalin-2(1H)-ones are present in a variety of natural products and can be widely found in pharmaceutical molecules with antimicrobial, antifungal, antithrombotic, and antitumor activities, etc. [1] Quinoxalin-2(1H)-one skeleton can also be utilized as a building block in the design of fluorescent dye and fluorogenic probe. [2] A series of active quinoxalinone derivatives bearing a C3-substituted group has been extensively studied, due to their diverse biological activities. [3] Therefore, the synthesis of C3-substituted quinoxalin-2(1H)-ones has gained much attention in recent years. One of the most efficient methods to access C3-substituted quinoxalin-2(1H)-ones is the direct transformation of quinoxalin-2(1H)-ones without prefunctionalization. [4] The past years have witnessed extensive efforts on the direct C3 arylation, [5] heteroarylation, [6] alkylation, [7] trifluoromethylation, [8a] trifluoroalkylation, [8b] difluoromethylation, [8c] acylation, [9] amination, [10] alkoxylation, [11a] fluoroalkoxylation, [11b] phosphonation [12] or sulfenylation [13] of quinoxalin-2(1H)-ones. Nevertheless, the introduction of a CN group to the C3-position of quinoxalin-2(1H)-ones is still highly desirable.Compounds containing cyano functional group, namely nitriles, are a valuable class of organic compounds due to their wide application in pharmaceuticals, agrochemicals, and materials, etc. [14] Moreover, nitriles are easily converted to other important organic compounds such as amides, carboxylic acids, esters, amines, ketones, aldehydes, etc. via the cyano transformation. [15] Therefore, the facile introduction of a cyano group to organic compounds is synthetically attractive for organic chemists. Chelation-assisted transition-metal-catalyzed CÀ H activation has been well developed for the CÀ H cyanation of arenes [16] or heteroarenes [17] in the past decade (Scheme 1a). However, this strategy required the introduction of directing groups to the substrates and the utilization of expensive Rh, Ru or Pd, etc. transition-metal catalysts. [18] Direct CÀ H cyanation of arenes [19] or heteroarenes [20] is an alternative and efficient protocol because it enables the formation of cyanated products without the prefunctionalization of substrates. In these reactions, the choice of cyano sources was significant for obtaining high efficiency. Electrophilic cyanating reagents, such as BrCN, [19a] N-cyano-N-phenyl-p-toluenesulfonamide (NCTS), [19e,20b] could smoothly react with electron-rich arenes. However, these reagents had some di...

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Section: Methodsmentioning

confidence: 99%

Electrochemical Oxidative C−H Cyanation of Quinoxalin‐2(1H)‐ones with TMSCN

Zhan

Tong

et al. 2021

Eur J Org Chem

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“…2019 年 Kiyokawa 和 Minakata 课题组 [45] 又采用类似的反应策略, 以末端联烯或环状 1,3-二烯为原料出发, 以 9-BBN 为硼氢化试剂, 在温和条件下反应首先制备烯丙基硼中间体, 之后以 N-Ts 氰胺或 TsCN 作为氰基化试剂, 发展了烯丙基硼的亲电氰基化反应, 为 β,γ-不饱和腈类化合物的合成提供了一种新的方法(Scheme 31). 同年, 赵万祥等 [46] 以 N-Ts 氰胺作为亲电氰基化试剂, 发展了路易斯酸催化酚类化合物的氰基化反应 (Scheme 32). 在氯化锡及二异丙胺的作用下(反应条件 A), 2-萘酚类底物可以高选择性的实现 C1 位氰基化, 但在相同反应条件下, 1-萘酚底物产率较低.…”

Section: 钌催化的亲电氰基化反应unclassified

Research and Application of N-Ts Cyanamides in Organic Synthesis

Wang¹,

Ma²,

Hou³

et al. 2023

Chinese Journal of Organic Chemistry

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N-Ts cyanamide, which has been widely used in the construction of nitrogen-containing framework, is one of the efficient and practical multifunctional synthetic precursors in organic synthesis. The progress in application of N-Ts cyanamide according to the reaction types is summarized, including the application in cyanation, cyclization reaction via cyanamide anion, cyanamidation, sulfonylation and cyclization reaction via cyano-group. The future development direction of this field is also prospected.

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“…On the other hand, 3-(3-oxobutyl)phthalides 5 are obtained by the reaction of compound 1 with methyl vinyl ketone (2b) as the sole products (Scheme 3). The synthesis of naththalene-1-ols [7][8][9] and 3-substituted phthalides [10][11][12][13][14][15][16] is attracting much attention, since bioactive compounds possessing these structures are known. This method has the potential to be applied to synthesize bioactive 2-cyanonaphthalen-1-ols [8,9] and 3-substituted phthalides [12][13][14][15][16].…”

Section: Introductionmentioning

confidence: 99%

“…The synthesis of naththalene-1-ols [7][8][9] and 3-substituted phthalides [10][11][12][13][14][15][16] is attracting much attention, since bioactive compounds possessing these structures are known. This method has the potential to be applied to synthesize bioactive 2-cyanonaphthalen-1-ols [8,9] and 3-substituted phthalides [12][13][14][15][16]. The reaction mechanisms of the electroreductive coupling of 1 with 2 and subsequent rearrangement to 3 are also discussed.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Electroreductive coupling of 2-acylbenzoates with α,β-unsaturated carbonyl compounds: density functional theory study on product selectivity

Kise¹,

Sakurai²

2022

Beilstein J. Org. Chem.

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The electroreductive coupling of 2-acylbenzoates with acrylonitrile in the presence of TMSCl and successive treatment with 1 M HCl gave 2-cyanonaphthalen-1-ols or 3-(3-cyanoethyl)phthalides. On the other hand, the reaction of 2-acylbenzoates with methyl vinyl ketone under the same conditions produced 3-(3-oxobutyl)phthalides as the sole products. What determines the product selectivity was studied using DFT calculations.

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Lewis Acid‐Mediated Cyanation of Phenols Using N‐Cyano‐N‐phenyl‐p‐toluenesulfonamide

Cited by 10 publications

References 46 publications

Electrochemical Oxidative C−H Cyanation of Quinoxalin‐2(1H)‐ones with TMSCN

Electrochemical Oxidative C−H Cyanation of Quinoxalin‐2(1H)‐ones with TMSCN

Research and Application of N-Ts Cyanamides in Organic Synthesis

Electroreductive coupling of 2-acylbenzoates with α,β-unsaturated carbonyl compounds: density functional theory study on product selectivity

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