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Synlett
Volumn , Issue 18, 2007, Pages 2912-2918
Facile generation and synthetic utility of nitrogen-centered aziridinyl radicals
Author keywords

haloaziridines; Aziridine ring opening; N aziridinyl radicals; Nucleophilic substitution; Piperazine synthesis
Indexed keywords

AZIRIDINYLBENZOQUINONE DERIVATIVE; NITROGEN; PIPERAZINE; RADICAL;
EID: 36549074050     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2007-990960     Document Type: Article
Times cited : (7)
References (26)
  • 12
    • 36549053456 scopus 로고    scopus 로고
    • Typical Procedure for the NXS-Facilitated N-Aziridinyl Radical Reaction with Olefins In a flame-dried Schlenk flask, equipped with septum, magnetic stir bar, and nitrogen inlet, were placed NIS (235 mg, 1.33 mmol, powdered 4 Å MS (200 mg, anhyd CH2Cl2 (10 mL) under nitrogen atmosphere at 0°C. After 10 min, aziridine-2-carboxylate methyl ester (100 μL, 1.11 mmol) was added via syringe. After 30 min, when TLC showed no aziridine remaining, 2-bromostyrene (138 μL, 1.11 mmol) was added via syringe. The reaction mixture was allowed to warm up to r.t. and stirred for 8 h. When TLC showed no methyl 1-iodoaziridine-2-carboxylate remaining, the reaction mixture was filtered and concentrated in vacuo, the residue oil was subjected to chromatography on silica gel, eluted with hexane-EtOAc (60:40, to give the product as light yellow oil. Methyl 1-[2-(2-Bromophenyl)-2-iodoethyl]aziridine-2-carboxylate (4) Yield 96, First diaste
    • 3): δ = 170.8, 140.7, 133.4, 130.1, 130.0, 128.4, 122.9, 67.7, 52.5, 38.3, 33.8, 27.5.
  • 17
    • 36549008949 scopus 로고    scopus 로고
    • In a flame-dried Schlenk flask, equipped with septum, magnetic stir bar, and nitrogen inlet, were placed NIS (1.2 equiv, powdered 4 Å MS (180 mg/mol aziridine, anhyd CH2Cl2 (0.11 mmol/mL) under nitrogen atmosphere at 0 0C Aziridine-2-carboxylate methyl ester (1.0 equiv) was added via syringe. After 30 min, when TLC showed no aziridine remaining, galvinoxyl (1.0 equiv) was added, followed by the addition of styrene. The reaction mixture was allowed to warm up to r.t. and stirred for 8 h. A control experiment was set up at the same time to compare the effect of the radical trap. After 8 h, the control experiment in the absence of galvinoxyl proceeded smoothly and the anti-Markovnikov product was afforded, while no desired product was formed in the presence of galvinoxyl
    • 2 (0.11 mmol/mL) under nitrogen atmosphere at 0 0C Aziridine-2-carboxylate methyl ester (1.0 equiv) was added via syringe. After 30 min, when TLC showed no aziridine remaining, galvinoxyl (1.0 equiv) was added, followed by the addition of styrene. The reaction mixture was allowed to warm up to r.t. and stirred for 8 h. A control experiment was set up at the same time to compare the effect of the radical trap. After 8 h, the control experiment in the absence of galvinoxyl proceeded smoothly and the anti-Markovnikov product was afforded, while no desired product was formed in the presence of galvinoxyl.
  • 18
    • 36549014988 scopus 로고    scopus 로고
    • Typical Procedure for the Nucleophilic Substitution of β-Haloaziridines with Amines To a mixture of 4 (50 mg, 0.122 mmol) and DMF (2.5 mL) was added allylamine (91.5 μL, 12.2 mmol) at r.t. and the mixture stirred for 12 h. When TLC showed no 4 remaining, H 2O (4 mL) and Et2O (2 mL) were added, the layers were then separated. The ether layer was washed with H2O followed by drying over Na2SO4. The solvent was removed in vacuo and the oily residue was subjected to chromatography on alumina, eluted with hexane-EtOAc (80:20, to give the product 15 as light yellow oil. Methyl 1-[2-Allylamino-2-(2-bromophen-yl)ethyl]aziridine-2-carboxylate (15) Yield 75, 1H NMR (400 MHz, CDCl3, δ, 7.63-7.62 (m, 1 H, 7.52-749 (m, 1 H, 7.32-7.28 (m, 1 H, 7.13-7.09 (m, 1 H, 5.92-5.84 (m, 1 H, 5.19-5.06 (m, 2 H, 4.34-4.31 (m, 1 H, 3.71 (s, 3 H, 3.12-3.07 (m, 2 H, 2.76-2.71 m
    • 3): δ = 171.5, 139.4, 134.8, 134.7, 133.0, 129.5, 129.4, 128.3, 128.3, 127.9, 123.1, 123.1, 117.1, 117.0, (79.9, 79.62), (70.5, 70.3), (65.3, 65.2), (52.3, 52.2), (39.1, 36.7), (35.4, 32.8).
  • 25
    • 36549003010 scopus 로고    scopus 로고
    • Fink, D. M.; Smith, H. K. Aventis Pharma Inc. (USA) WO2006086705, 2006.
    • Fink, D. M.; Smith, H. K. Aventis Pharma Inc. (USA) WO2006086705, 2006.
  • 26
    • 36549040339 scopus 로고    scopus 로고
    • Procedure for the Synthesis of 30 In a 5 mL Schlenk tube, equipped with septum and magnetic stir bar, were placed 19 (0.1 mmol, K 2CO3 (0.22 mmol, and anhyd MeCN (1 mL, Oxalyl chloride was added via syringe and the solution was stirred at 60°C for 2 h. When TLC showed no starting material remaining, the solution was filtered and the filtrated was washed with H2O. The organic layer was dried over anhyd Na2SO4 and filtered. The filtrated was concentrated in vacuo and the light brown residue was directly used in the next step without purification. Reduction with LiAlH4 To a suspension of 300 mg LiAlH4 (7.91 mmol) in 40 mL THF, 264 mg crude product of diketopiperazine 29 (0.66 mmol) dissolved in 5 mL THF was added. The mixture was stirred at 60°C for 12 h. After cooling to 0°C, H 2O (0.4 mL, 15% NaOH (0.4 mL, and H2O (0.4 mL) were added dropwise wh
    • 3): δ = 141.9, 139.1, 129.0, 128.9, 128.8, 128.4, 128.2, 127.9, 127.0, 67.6, 64.9, 62.3, 59.1, 53.6, 51.9, 27.2, 9.7.

* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.