Ruthenium‐Catalyzed C–H Selenylations of Benzamides

Ma, Wenbo; Weng, Zhengyun; Fang, Xinyue; Gu, Linghui; Song, Yupin; Ackermann, Lutz

doi:10.1002/ejoc.201801532

Cited by 39 publications

(15 citation statements)

References 92 publications

(25 reference statements)

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“…The more steric hindrance 2-aryl acetamides and electron-efficient diselenide substrates also remains a challenge. In continuation of our work [14] and those of others on the catalytic synthesis of unsymmetrical diaryl selenides, herein, we disclose the efficient palladium (II)-catalyzed ortho-selenylations of synthetically useful aryl acetic amide with…”

Section: Full Papermentioning

confidence: 70%

Palladium‐Catalyzed Distal C−H Selenylation of 2‐Aryl Acetamides with Diselenides and Selenyl Chlorides

Tan

et al. 2020

Adv Synth Catal

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A convenient and effective method of palladium-catalyzed CÀ H selenylation of the 2-aryl acetamides assisted with removable 8-aminoquinoline with readily available diselenides and selenyl chlorides has been developed. This selenylation reaction is scalable and tolerates a wide range of functional groups, providing a straightforward way of the preparing unsymmetrical diaryl selenides and dibenzoselene-pinone. Preliminary mechanistic studies indicated that a single-electron transfer type mechanism and facile CÀ H metalation are operative.

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Section: Full Papermentioning

confidence: 70%

Palladium‐Catalyzed Distal C−H Selenylation of 2‐Aryl Acetamides with Diselenides and Selenyl Chlorides

Tan

et al. 2020

Adv Synth Catal

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“…N-cyclohexyl-2-(phenylselanyl)benzamide 12b Yield: 60%; mp 183–185 °C (lit. [ 22 ] mp 179–181 °C); 1 H NMR (400 MHz, CDCl 3 ) δ = 1.21–1.31 (m, 3H), 1.40–1.50 (m, 2H, CH 2 ), 1.65–1.69 (m, 1H), 1.74–1.80 (m, 2H, CH 2 ), 2.05–2.09 (m, 2H, CH 2 ), 3.97–4.07 (m, 1H, N-CH), 5.32 (bs, 1H, NH), 7.09–7.11 (m, 1H ar ), 7.17–7.23 (m, 2H ar ), 7.35–7.41 (m, 3H ar ), 7.50–7.54 (m, 1H ar ), 7.60–7.65 (m, 2H ar ); 13 C NMR (100.6 MHz, CDCl 3 ) δ = 24.83 (2 × CH 2 ), 25.55 (CH 2 ), 33.07 (2 × CH 2 ), 48.87 (CH), 125.76 (CH ar ), 127.33 (CH ar ), 128.42 (CH ar ), 129.55 (2 × CH ar ), 130.01 (C ar ), 130.80 (CH ar ), 131.26 (CH ar ), 134.60 (C ar ), 135.04 (C ar ), 135.88 (2 × CH ar ), 167.38 (C=O); 77 Se NMR (76 MHz, CDCl 3 ) δ = 434.17 ppm; IR: 3251, 3053, 2924, 2849, 1618, 1583, 1541, 1459, 1448, 1436, 1377, 1337, 1299, 1283, 1256, 1240, 1191, 1149, 1120, 1081, 1066, 1030, 1018 cm −1 ; Elemental Anal. Calcd for C 19 H 21 NOSe (359.08): C, 63.68; H, 5.91; N, 3.91 Found: C, 63.52; H, 5.86; N, 3.83.…”

Section: Methodsmentioning

confidence: 99%

Phenylselanyl Group Incorporation for “Glutathione Peroxidase-Like” Activity Modulation

et al. 2020

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The ability of organoselenium molecules to mimic the activity of the antioxidant selenoenzyme glutathione peroxidase (GPx) allows for their use as antioxidant or prooxidant modulators in several diseases associated with the disruption of the cell redox homeostasis. Current drug design in the field is partially based on specific modifications of the known Se-therapeutics aimed at achieving more selective bioactivity towards particular drug targets, accompanied by low toxicity as the therapeutic window for organoselenium compounds tends to be very narrow. Herein, we present a new group of Se-based antioxidants, structurally derived from the well-known group of GPx mimics—benzisoselenazol-3(2H)-ones. A series of N-substituted unsymmetrical phenylselenides with an o-amido function has been obtained by a newly developed procedure: a copper-catalyzed nucleophilic substitution by a Se-reagent formed in situ from diphenyl diselenide and sodium borohydride. All derivatives were tested as antioxidants and anticancer agents towards breast (MCF-7) and leukemia (HL-60) cancer cell lines. The highest H2O2-scavenging potential was observed for N-(3-methylbutyl)-2-(phenylselanyl)benzamide. The best antiproliferative activity was found for (−)-N-(1S,2R,4R)-menthyl-2-(phenylselanyl)benzamide (HL-60) and ((−)-N-(1S,2R,3S,6R)-(2-caranyl))benzamide (MCF-7). The structure–activity correlations, including the differences in reactivity of the obtained phenyl selenides and corresponding benzisoselenazol-3(2H)-ones, were performed.

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“…Ackermann, Ma, and co-workers reported a ruthenium-catalyzed CÀ H selenylation of benzamides providing the monoselenylated products in good to excellent yields. [31] In addition to selective mono-selenylated products which were obtained in good yields via CÀ H metal-catalyzed activation, the authors demonstrated that the directing group can be removed under mild reaction conditions, affording compounds that can be applied in medicinal chemistry. Recently, Nakamura, Shang, and co-workers described a procedure for chromium-catalyzed C(sp 2 )À H functionalization of ortho-position of secondary amides in the presence of trimethylaluminum as a base, for the selective formation of alkynylated products.…”

Section: Monodentate N-based Groupsmentioning

confidence: 99%