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Volumn , Issue 13, 2009, Pages 2172-2176

Synthesis of the disubstituted maleic anhydride frame using a novel tandem radical-polar reaction

Author keywords

Cyclizations; Imides; Radical reactions; Sulfur; Tandem reactions

Indexed keywords

1 [3 [[[3 (3 ETHYL 4 METHYL 2,5 DIOXO 2,5 DIHYDRO 1H PYRROL 1 YL)PROPYL]SULFONYL]SULFANYL]PROPYL] 3 ETHYL 4 METHYL 1H PYRROLE 2,5 DIONE; 3 (2,2 DICHLOROBUTANOYL) 2 ETHYLIDENE 1,3 THIAZINE; 3 (2,2 DICHLOROBUTANOYL) 2 ETHYLIDENE 1,3 THIAZOLIDINE; CUPROUS ION; MALEIC ANHYDRIDE; PYRROLE DERIVATIVE; THIAZOLIDINE DERIVATIVE; UNCLASSIFIED DRUG;

EID: 68949100621     PISSN: 09365214     EISSN: 14372096     Source Type: Journal    
DOI: 10.1055/s-0029-1217569     Document Type: Article
Times cited : (10)

References (36)
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    • For the sake of completeness the question is debated, since recent computational studies on the cyclization of N-vinylcarbamoyl methyl radicals suggest that the 5-endo mode is not only thermodynamically favored, but also kinetically favored: Chatgilialoglu, C.; Ferreri, C.; Guerra, M.; Timokhin, V.; Froudakis, G.; Gimisis, T. J. Am. Chem. Soc. 2002, 124, 10765.
    • For the sake of completeness the question is debated, since recent computational studies on the cyclization of N-vinylcarbamoyl methyl radicals suggest that the 5-endo mode is not only thermodynamically favored, but also kinetically favored: Chatgilialoglu, C.; Ferreri, C.; Guerra, M.; Timokhin, V.; Froudakis, G.; Gimisis, T. J. Am. Chem. Soc. 2002, 124, 10765.
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    • besides Cu(I, Ru(II) has also been significantly employed
    • Clark, A. J. Chem. Soc. Rev. 2002, 31, 1; besides Cu(I), Ru(II) has also been significantly employed.
    • (2002) Chem. Soc. Rev , vol.31 , pp. 1
    • Clark, A.J.1
  • 18
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    • The radical-polar crossover has also been proposed for Ni, Mn(III), Bu3SnH, and Ce(IV) promoted RC of enamides: (a) Cassayre, J.; Quiclet-Sire, B.; Saunier, J.-B.; Zard, S. Z. Tetrahedron 1998, 54, 1029.
    • The radical-polar crossover has also been proposed for Ni, Mn(III), Bu3SnH, and Ce(IV) promoted RC of enamides: (a) Cassayre, J.; Quiclet-Sire, B.; Saunier, J.-B.; Zard, S. Z. Tetrahedron 1998, 54, 1029.
  • 29
    • 68949124004 scopus 로고    scopus 로고
    • 3-(2,2-Dichlorobutanoyl)-2-ethylidene-1,3-thiazolidine (5a) Yellow oil. Rf, 0.64 (PE-Et2O, 1:1, 1H NMR (200 MHz, CDCl3, δ, 1.23 (t, J, 7.1 Hz, 3 H, CH 3, 1.74 (d, J, 6.8 Hz, 3 H, CH3, 2.50 (q, J, 7.1 Hz, 2 H, CH2, 3.05 (t, J, 6.2 Hz, 2 H, CH2, 4.48 (t, J, 6.2 Hz, 2 H, CH2, 6.26 (q, J, 7.1 Hz, 1 H, CH) ppm. 13C NMR (50 MHz, CDCl3, δ, 9.6, 15.8, 28.1, 39.4, 53.1, 87.2, 109.1, 135.0, 162.3 ppm. MS (EI, 70 eV, m/z, 253 (22, M, 218 (100, 190 (28, IR (film, 1670 (C=O) cm-1. 3-(2,2-Dichlorobutanoyl)-2-ethylidene-1,3- thiazine (5b) Yellowish oil. Rf, 0.56 (PE-Et 2O, 1:1, 1H NMR (400 MHz, CDCl3, δ, 1.19 (t, J, 7.1 Hz, 3 H, CH3, 1.84 d, J, 6.8 Hz, 3 H, CH
    • -1.
  • 31
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    • Typical Procedure for the ATRC Compound 5b (2 mmol, 536 mg, CuCl (10 mol, 20 mg, and Na2CO3 (2 mmol, 212 mg) were weighed into a Schlenk tube, then dry MeCN (3 mL) and TMEDA (20 mol, 60 μL) were added under Ar. The mixture was stirred at 30°C and after 17 h diluted with H2O and extracted with CH2Cl2 (3 x 25 mL, The combined organic layers were concentrated under vacuum. Chromatography of the crude product on silica, eluting with a PE-Et2O gradient from 9:1 to 4:6, afforded 1-{3, 7-ethyl-8-methyl-6-oxo-3,4-dihydro- 2H-pyrrolo[ 2,1-b][1,3]thiazin-6 (8aH)-yl)sulfanyl]propyl, 3-ethyl-4-methyl-1H-pyrrole-2,5-dione (13b) as yellow oil (327 mg, 80, and 1,1′-(disulfanediyldipropane-2,1-diyl)bis(3-ethyl-4-methyl- 1H-pyrrole-2,5-dione, 14b) as orange oil (60 mg, 14, Compound 13b: Rf, 0.12 PE-Et2O, 1:1
    • 13C NMR, HRMS, and IR) consistent with their structures.
  • 34
    • 68949129683 scopus 로고    scopus 로고
    • 1-[3, 3-(3-Ethyl-4-methyl-2,5-dioxo-2,5-dihydro-1Hpyrrol- 1-yl)propyl]sulfonyl}sulfanyl)propyl]-3-ethyl-4-methyl-1H-pyrrole-2, 5-dione (17) Yellow oil. Rf, 0.10 (PE-Et2O, 1:1, 1H NMR (400 MHz, CDCl3, δ, 1.11 (t, J, 7.6, 6 H, 2 CH3, 1.94 (s, 6 H,2 CH3, 2.00 (quin, J, 6.8 Hz, 2 H, CH2, 2.14 (quin, J, 7.2 Hz, 2 H, CH2, 2.38 (br q, J, 7.6 Hz, 4 H, 2 CH2, 3.07 (br t, J, 6.8 Hz, 2 H, CH2, 3.31 (br t, J, 7.2 Hz, 2 H, CH2, 3.57 (br t, J, 6.8 Hz, 2 H, CH2, 3.61 (br t, J, 7.2 Hz, 2 H, CH2) ppm. 13C NMR 100 MHz, CDCl3, d, 8.4, 12.5, 17.0, 23.4, 28.9, 33.5, 35.8, 36.1, 60.2, 136.6, 136.7, 142.28, 142.32, 171.6, 171.7, 172.0, 172.1 ppm. HRMS: m/z calcd for C20H29N2O6
    • -1.
  • 35
    • 68949102681 scopus 로고    scopus 로고
    • Compound 13b (0.73 mmol, 300 mg, wet SiO2 60, w/w, 365 mg, NaNO3 (1.46 mmol, 124 mg, and silica-sulfuric acid (1.46 mmol, 400 mg) were weighed into a vial, then CH2Cl2 (3 mL) was added. The vial was closed with a screw cap, and the mixture was stirred at 45°C for 17 h and then cooled down to r.t. Et2O (10 mL) was added, and the suspension was stirred at r.t. for 30 min and then filtered. The solid was washed with Et2O (3 x 10 mL, then the combined organic layers were concentrated under vacuum into a Schlenk tube. Glacial AcOH (1.5 mL) and 2 M aq H2SO4 (1.5 mL) were added to the crude product, then the tube was closed with a screw cap. The mixture was stirred at 140°C for 65 h and then cooled down to r.t. Water (15 mL) was added, and the solution was extracted with Et2O 4 x 20 mL, The solvent was removed under vacuum. Chromatography of the crude product on silica, elu
    • 2O gradient from 9:1 to 5:5, afforded 3-ethyl-2-methyl maleic anhydride (12, 61 mg, 60%). Characterizations were in agreement with literature values: Poigny, S.; Guyot, M.; Samadi, M. J. Chem. Soc., Perkin Trans. 1 1997, 2175.


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