Radical-Induced Formation of Some Siloles and Diazasiloles

Ding, Bangwei; Teng, Zhu; Keese, Reinhart

doi:10.1021/jo0202684

Cited by 9 publications

(3 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…91 Purified by column chromatography using acetone and ethyl acetate in a 1:1 ratio as eluants using general procedure C. Yield 54% (1.17 g); brown solid; mp 71−73 °C; N,N′-Diallylbenzene-1,2-diamine (1l). 100 Purified by column chromatography using hexanes and ethyl acetate in a 10:1 ratio as eluants using general procedure A. Yield 24% (1.35 g); brown liquid; N,N′-Diethylbenzene-1,2-diamine (1m).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…N-(4-Methylbenzyl)benzene-1,2-diamine (5d). 100 Purified by column chromatography using hexanes and ethyl acetate in a 5:1 ratio as eluants using general procedure A. Yield 56% (3.5 g); brown liquid; 1 H NMR (500 MHz, CDCl 3 ) δ 7.30 (d, J = 7.7 Hz, 2H), 7.18 (d, J = 7.7 Hz, 2H), 6.82 (t, J = 7.5 Hz, 1H), 6.77−6.67 (m, 6H), 4.28 (s, 2H), 3.43 (br, 3H), 2.37 (s, 3H; 13 C{ 1 H} NMR (125 MHz, CDCl 3 ) δ 137.9, 137.0, 136.4, 134.2, 129.4, 127.9, 120.8, 118.8, 116.5, 112.0, 48.5, 21.2; IR (neat, cm −1 ): 3387, 3358, 3261, 3091, 2911, 1549.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

See 1 more Smart Citation

1,2-Disubstituted Benzimidazoles by the Iron Catalyzed Cross-Dehydrogenative Coupling of Isomeric o-Phenylenediamine Substrates

et al. 2020

View full text Add to dashboard Cite

Benzimidazoles are common in nature, medicines, and materials. Numerous strategies for preparing 2-arylbenzimidazoles exist. In this work, 1,2-disubstituted benzimidazoles were prepared from various mono-and disubstituted ortho-phenylenediamines (OPD) by iron-catalyzed oxidative coupling. Specifically, O 2 and FeCl 3 •6H 2 O catalyzed the cross-dehydrogenative coupling and aromatization of diarylmethyl and dialkyl benzimidazole precursors. N,N′-Disubstituted-OPD substrates were significantly more reactive than their N,N-disubstituted isomers, which appears to be relative to their propensity for complexation and charge transfer with Fe 3+ . The reaction also converted N-monosubstituted OPD substrates to 2-substituted benzimidazoles; however, electron-poor substrates produce 1,2-disubstituted benzimidazoles by intermolecular imino-transfer. Kinetic, reagent, and spectroscopic (UV−vis and EPR) studies suggest a mechanism involving metal−substrate complexation, charge transfer, and aerobic turnover, involving high-valent Fe(IV) intermediates. Overall, comparative strategies for the relatively sustainable and efficient synthesis of 1,2-disubstituted benzimidazoles are demonstrated.

show abstract

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

1,2-Disubstituted Benzimidazoles by the Iron Catalyzed Cross-Dehydrogenative Coupling of Isomeric o-Phenylenediamine Substrates

et al. 2020

View full text Add to dashboard Cite

show abstract

“…In the synthesis of seven-membered silacycles, formation of the C−Si bonds often relies on nucleophilic attack on a chlorosilane. 8 The construction of seven-membered silacycles by isomerization through [3.2.0] ring-opening using flash vacuum pyrolysis (FVP), 9 radical cyclization, 10 isomerization via silacyclobutane ring-opening, 11 olefin metathesis using Grubbs first catalyst, 12 and intramolecular hydrosilylation 13 has also been reported (see Supporting Information, Scheme S1). However, these conventional methods, except FVP, afford the corresponding seven-membered silacycles in low to moderate yields.…”

mentioning

confidence: 99%