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Volumn 26, Issue 26, 2007, Pages 6511-6514

Calix[4]pyrrole as a promoter of the CuCl-catalyzed reaction of styrene and chloramine-T

Author keywords

[No Author keywords available]

Indexed keywords

ACETONITRILE; CHEMICAL ACTIVATION; COPPER COMPOUNDS; REACTION RATES; STYRENE; TRACE ANALYSIS;

EID: 38049150123     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om700958c     Document Type: Article
Times cited : (22)

References (43)
  • 5
    • 35948942795 scopus 로고    scopus 로고
    • As defined for the purposes of this paper, an anion receptor is a synthetic system that achieves recognition through a combination of non-metal-based electrostatic interactions and hydrogen bonds. After submission of the manuscript an interesting report appeared wherein the authors used a thiourea receptor to catalyze an asymmetric Pictet-Spengler-type ring closure Raheem, I. T.; Thiara, P. S.; Peterson, E. A.; Jacobsen E. N. J. Am. Chem. Soc. 2007, 129, 13404-13405.
    • As defined for the purposes of this paper, an anion receptor is a synthetic system that achieves recognition through a combination of non-metal-based electrostatic interactions and hydrogen bonds. After submission of the manuscript an interesting report appeared wherein the authors used a thiourea receptor to catalyze an asymmetric Pictet-Spengler-type ring closure (Raheem, I. T.; Thiara, P. S.; Peterson, E. A.; Jacobsen E. N. J. Am. Chem. Soc. 2007, 129, 13404-13405.
  • 7
    • 0346865819 scopus 로고    scopus 로고
    • Considerable effort has been devoted of late to the generation of supramolecular receptor systems that can promote reactions through hydrogen-bonding interactions with a range of non-anion-releasing substrates (e.g., carbonyl activation). For recent reviews, see: Schreiner, P. R
    • (a) Considerable effort has been devoted of late to the generation of supramolecular receptor systems that can promote reactions through hydrogen-bonding interactions with a range of non-anion-releasing substrates (e.g., carbonyl activation). For recent reviews, see: Schreiner, P. R Chem. Soc. Rev. 2003, 32, 289-296.
    • (2003) Chem. Soc. Rev , vol.32 , pp. 289-296
  • 26
    • 0032578675 scopus 로고    scopus 로고
    • For examples of I2-catalyzed aziridinations of alkenes using chloramine-T, see: Ando, T, Kano, D, Minakata, S, Ryu, I, Komatsu, M. Tetrahedron 1998, 54, 13485-13494
    • 2-catalyzed aziridinations of alkenes using chloramine-T, see: Ando, T.; Kano, D.; Minakata, S.; Ryu, I.; Komatsu, M. Tetrahedron 1998, 54, 13485-13494.
  • 31
    • 3042790242 scopus 로고    scopus 로고
    • Similar effects have been seen with bromamine-T and iron(III) porphyrins; see: Vyas, R; Gao, G.-Y.; Harden, J. D.; Zhang, P Org. Lett. 2004, 6, 1907-1910.
    • (a) Similar effects have been seen with bromamine-T and iron(III) porphyrins; see: Vyas, R; Gao, G.-Y.; Harden, J. D.; Zhang, P Org. Lett. 2004, 6, 1907-1910.
  • 32
    • 23044479258 scopus 로고    scopus 로고
    • 7, More complex chemistry is seen in the case of Mn(V) corrole-promoted ArI=NTs aziridinations;
    • (b) Gao, G.-Y.; Harden, J. D.; Zhang, P. Org. Lett. 2005, 7, 3191-3193. More complex chemistry is seen in the case of Mn(V) corrole-promoted ArI=NTs aziridinations;
    • (2005) Org. Lett , pp. 3191-3193
    • Gao, G.-Y.1    Harden, J.D.2    Zhang, P.3
  • 37
    • 38049175941 scopus 로고    scopus 로고
    • Calixpyrroles, in their neutral, NH forms, generally do not ligate to transition metals. These forms are stable in the absence of all but the most basic conditions. Hence, we believe it is unlikely that the calix[4]pyrrole of this study is functioning as a ligand for Cu and facilitating the aziridination reaction through processes involving metal coordination. This is corroborated by comparison of entries 12 and 13 in Table 1.
    • (d) Calixpyrroles, in their neutral, NH forms, generally do not ligate to transition metals. These forms are stable in the absence of all but the most basic conditions. Hence, we believe it is unlikely that the calix[4]pyrrole of this study is functioning as a ligand for Cu and facilitating the aziridination reaction through processes involving metal coordination. This is corroborated by comparison of entries 12 and 13 in Table 1.
  • 38
    • 38049163311 scopus 로고    scopus 로고
    • Two general procedures were used. Procedure A: For benchtop work, a Schlenk flask was loaded with CuCl (2 mg, 0.020 mmol, calix[4]pyrrole (9 mg, 0.020 mmol, hexamethylbenzene (9 mg, 0.055 mmol, and a PTFE-coated stirbar in a drybox. The flask was stoppered with a rubber septum, taken out of the box, and attached to a vacuumnitrogen line, and acetonitrile (20 mL) was injected. Styrene (580 μL) was injected via microsyringe. Under a stream of N 2, chloramine-T was added in one portion. Immediately, the mixture underwent several color changes, finally becoming green. After the desired time, a 1 mL aliquot of the solution was filtered through a 2 cm column of diatomaceous earth packed with dichloromethane, with 20 mL of dichloromethane being used to complete the elution. The filtrate solution was vacuum-dried, and the residue was dissolved in 0.5 mL of CDCl3 and analyzed by 1H NMR, spectroscopy, integrating the signals of the aziridine product [1
    • 2. Remaining insoluble material was removed by filtration through alumina. Purification using column chromatography (silica gel, 1:4 EtOAc/hexanes as eluent) afforded 1.3 g (49% yield) of the aziridine product as a white crystalline solid. Spectro-scopic data were consistent with the product obtained from procedure A.
  • 40
    • 38049133359 scopus 로고    scopus 로고
    • 1,9-Bisformyl-5,5-dimethyldipyrromethane23 (1.5 g, 6.5 mmol) and KOH (2.60 g, 46.3 mmol) in ethylene glycol (40 mL) and hydrazine hydrate (1.80 g, 56.3 mmol) were heated at reflux for 2 h. The reaction mixture was cooled to room temperature and diluted with CH2Cl2 (50 mL) and water (50 mL, and the aqueous layer was extracted with additional CH 2Cl2 (50 mL, The organic layers were combined and dried (Na2SO4, and the CH2Cl2 was removed under vacuum to afford an off-white powder (1.05 g, 80, 1H NMR (CDCl3) δ 1.59 (s, 3H, 2.17 (s, 3H, 5.75-5.78 (m, 1H, 5.92-5.94 (m, 1H, 7.48 (br, 1H, 13C NMR (CDCl3) δ 13.0, 29.2, 35.2, 103.5, 105.2, 126.9, 137.9; HRMS (CI, caled 202.1470, obsd 202.1473 C13H18N2
    • 2).
  • 43
    • 0000303283 scopus 로고    scopus 로고
    • A dependence on the oxidation state of the precatalyst, Cu(I) or Cu(II), is not typically seen; see : Evans, D.; Faul, M. M.; Bilodeau, M. T.; Anderson, B. A.; Barnes, D. M J. Am. Chem. Soc. 1993, 115, 5328-5329.
    • A dependence on the oxidation state of the precatalyst, Cu(I) or Cu(II), is not typically seen; see : Evans, D.; Faul, M. M.; Bilodeau, M. T.; Anderson, B. A.; Barnes, D. M J. Am. Chem. Soc. 1993, 115, 5328-5329.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.