A Novel Synthesis of Benzo[<i>b</i>]selenophenes via Regioselective Intramolecular Transformation of 4-(3-Nitroaryl)-1,2,3-selenadiazoles

Lyapunova, Anna G.; Petrov, M. L.; Androsov, D. A.

doi:10.1021/ol400547n

Cited by 17 publications

(12 citation statements)

References 41 publications

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“…Nucleophilic substitution of hydrogen in electron‐deficient arenes has been extensively studied since the late 1970s 1–3 . Addition of nucleophilic agents to electron‐deficient arenes such as nitroarenes proceeds readily to the positions occupied by hydrogen atom to form the corresponding σ H ‐adducts.…”

Section: Methodsmentioning

confidence: 99%

“…Addition of nucleophilic agents to electron‐deficient arenes such as nitroarenes proceeds readily to the positions occupied by hydrogen atom to form the corresponding σ H ‐adducts. Among various pathways for the conversion of σ H ‐adducts to products, direct substitution of hydrogen via vicarious nucleophilic substitution (VNS) and oxidative nucleophilic substitution of hydrogen (ONSH) pathways are most frequently used 1–3 …”

Section: Methodsmentioning

confidence: 99%

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Aerobic Transition‐Metal‐Free Synthesis of 2,3‐Diarylindoles and 5‐Aryluracils via Oxidative Nucleophilic Substitution of Hydrogen Pathway

Moon

Kim

et al. 2015

Bulletin Korean Chem Soc

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Aerobic Transition‐Metal‐Free Synthesis of 2,3‐Diarylindoles and 5‐Aryluracils via Oxidative Nucleophilic Substitution of Hydrogen Pathway

Moon

Kim

et al. 2015

Bulletin Korean Chem Soc

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“…As a next experiment, in order to obtain 3b as a major product, we examined the reaction of 1 and 2b in the presence of an oxidant KMnO 4 (2.0 equiv) 2c–e . The yield of 3b was increased to 91%, as expected, and 4b was formed in only a trace amount (Scheme ) .…”

Section: Methodsmentioning

confidence: 74%

“…Nucleophilic substitution reaction of hydrogen atom in electron‐deficient arenes has been extensively studied . An addition of nucleophile to electron‐deficient arenes such as nitroarene proceeds readily at the positions occupied by hydrogen atom to form σ H ‐adducts.…”

Section: Methodsmentioning

confidence: 99%

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Nucleophilic Aromatic tele‐Substitution of Hydrogen of 9‐Nitroanthracene with 2‐Naphthols and Phloroglucinol

Kim

Lim

Nam

et al. 2016

Bulletin Korean Chem Soc

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Nucleophilic substitution reaction of hydrogen atom in electron-deficient arenes has been extensively studied. [1][2][3] An addition of nucleophile to electron-deficient arenes such as nitroarene proceeds readily at the positions occupied by hydrogen atom to form σ H -adducts. Usually, the σ H -adducts can be converted to products either via a vicarious nucleophilic substitution (VNS) 1b,c or an oxidative nucleophilic substitution of hydrogen (ONSH). 1d Many oxidants have been used for the oxidation of σ H -adducts including an aerobic oxidation process with molecular oxygen. 2-4 Recently, Kumar et al. reported β-arylation of indole under an aerobic oxidation condition, as shown in Scheme 1. 3a Very recently, we also reported an aerobic ONSH reaction of nitroarenes with 2-arylindoles or uracil. 3b In addition, the aerobic ONSH reaction was extended to the intramolecular version of nitroarene bearing a nitroalkane tether by us, as also shown in Scheme 1. 3c Although the ONSH reaction has been studied extensively with various nitroarenes, the reaction of 9nitroanthracene (1) has not been studied much. 4 During our studies on ONSH reaction, 3b,c an aerobic ONSH reaction of 1 with indole (2a) was examined in the presence of Cs 2 CO 3 in DMSO under O 2 balloon atmosphere, as shown in Scheme 2. However, the yield of 3a (32%) was low presumably due to steric hindrance caused by the peri hydrogen atoms at 4-and 5-positions of 1. Thus, we examined the reaction of 1 with 2-naphthol (2b) under the same reaction conditions, because the C1-position of 2-naphthol has been proved to be highly nucleophilic in many reactions. 5 A successful C-C bond formation was observed; however, the result was quite surprising. Generally expected ONSH product 3b was obtained in low yield (22%) along with an unusual tele-substitution product 4b (63%) as a major product. 6,7 In a tele-substitution reaction, the nucleophile is attached to the position located by more than one atom from the atom to which the leaving group is attached. 6 In order to further reduce the amount of ONSH product 3b, the reaction was examined in DMF under N 2 balloon atmosphere. However, the yields of both 3b (9%) and 4b (55%) decreased. The reaction of 1 and 2b in DMSO in an open flask showed a similar result (see, entry 1 in Table 1) to that of the reaction carried out under O 2 balloon atmosphere (Scheme 2).Thus, we examined the reactions of 1 with 2-naphthol derivatives 2c-2f in DMSO in an open flask. The results are summarized in Table 1. The reaction of naphthalene-2,7-diol (2c, entry 2) afforded the corresponding tele-substitution products 4c (68%) as a major product along with a low yield of 3c (19%). In the reaction, the formation of 1,8-dianthracenyl derivative was not observed. A second introduction of anthracene moiety to 4c was not observed even in the presence of an excess amount of 1 presumably due to steric reason. The reaction with 7-methoxynaphthalene-2-ol (2d, entry 3) produced 4d in good yield (70%) along with 3d (9%). The reaction of 6-methoxynapht...

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Selenium(IV) Oxide

Hoekstra

Fairlamb

Giroux

et al. 2017

Encyclopedia of Reagents for Organic Synthesis

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A Novel Synthesis of Benzo[b]selenophenes via Regioselective Intramolecular Transformation of 4-(3-Nitroaryl)-1,2,3-selenadiazoles

Cited by 17 publications

References 41 publications

Aerobic Transition‐Metal‐Free Synthesis of 2,3‐Diarylindoles and 5‐Aryluracils via Oxidative Nucleophilic Substitution of Hydrogen Pathway

Aerobic Transition‐Metal‐Free Synthesis of 2,3‐Diarylindoles and 5‐Aryluracils via Oxidative Nucleophilic Substitution of Hydrogen Pathway

Nucleophilic Aromatic tele‐Substitution of Hydrogen of 9‐Nitroanthracene with 2‐Naphthols and Phloroglucinol

Selenium(IV) Oxide

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