25
S1 Supporting Information One-step Barton decarboxylation by micellar catalysis – application to the synthesis of maleimide derivatives Floriane Mangin, a Estelle Banaszak-Léonard a and Christophe Len a,b * a Sorbonne Universités, Université de Technologie de Compiègne, Ecole Supérieure de Chimie Organique et Minérale, EA 4297 Transformations Intégrées de la Matière Renouvelable, Centre de Recherche Royallieu, CS 60319, F-60203 Compiègne cedex, France. Fax: +33 (0)3 44 97 15 91; Tel: +33 (0)3 44 23 88 28; b Department of Chemistry, University of Hull, Hull HU6 7RX, England. E-mail: [email protected] Table of Contents General information S1 General procedure for the Barton decarboxylation S1 General procedure for maleimide formation S1 Spectral data of all compounds S2 – S6 NMR spectra of all compounds S7 – S23 General information All products were purchased either from Acros or Sigma Aldrich depending on their availability and were used without further purification. All solvents were purchased from Carlo Erba. Reactions were performed with an ultrasonic probe (Bioblock Scientific, Vibra cell 75042) and monitored by TLC (Kieselgel 60F254 MERCK aluminium sheet) with detection by UV light and/or phosphomolybdic acid solution and by HPLC (Shimazu). Flash column chromatography was performed on an automatic Grace apparatus, using 40 g connected silica gel cartridges. 1 H and 13 C NMR spectra were recorded on a 400 MHz Bruker UltraShield 400 MHz/54 mm Ultra long hold. Chemical shifts (δ) are quoted in ppm and are referenced to TMS as an internal standard. Coupling constants (J) are quoted in Hz. IR spectra were recorded on a Jasco FT/IR-4100 ATR. General procedure for the Barton decarboxylation In a 100 mL Beaker containing a Brij ® 30 aqueous solution (300 mg in 30 mL), 2-mercaptopyridine-N-oxide (150 mg, 1.2 mmol), DCC (250 mg, 1.2 mmol), N-phenylmaleimide (268 mg, 1.5 mmol) and carboxylic acid (1.03 mmol) were introduced. The mixture was sonicated 20 min in an ice bath (the ultrasonic probe was placed at 1cm from the bottom of the beaker to ensure a homogenous dispersion). The crude mixture was lyophilized and the residue was purified on flash chromatography (Cyclohexane/EtOAc 1/0 to 7/3). General procedure for maleimide formation In a 50 mL round bottom flask containing 1-phenylpyridin-2-ylthiopyrrolidine-2,5-dione (1 mmol) product in CH 2 Cl 2 (10 mL) was added m-CPBA (246 mg, 10 mmol) and the mixture is stirred for 10 min. at 0°C. Then saturated NaHCO 3 solution (30 mL) was added and the crude product extracted with CH 2 Cl 2 (30 mL). After the evaporation of the solvent, toluene (20 mL) was added and the media was heated under reflux for 1h. Toluene was evaporated and the crude mixture was purified on flash chromatography (Cyclohexane/EtOAc 1/0 to 7/3). Electronic Supplementary Material (ESI) for RSC Advances. This journal is © The Royal Society of Chemistry 2015

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  • S1

    Supporting Information

    One-step Barton decarboxylation by micellar catalysis – application to the synthesis of maleimide derivatives

    Floriane Mangin,a Estelle Banaszak-Léonarda and Christophe Lena,b*

    aSorbonne Universités, Université de Technologie de Compiègne, Ecole Supérieure de Chimie Organique et Minérale, EA 4297 Transformations Intégrées de la Matière Renouvelable, Centre de Recherche Royallieu, CS

    60319, F-60203 Compiègne cedex, France. Fax: +33 (0)3 44 97 15 91; Tel: +33 (0)3 44 23 88 28;

    bDepartment of Chemistry, University of Hull, Hull HU6 7RX, England.E-mail: [email protected]

    Table of ContentsGeneral information S1

    General procedure for the Barton decarboxylation S1

    General procedure for maleimide formation S1

    Spectral data of all compounds S2 – S6

    NMR spectra of all compounds S7 – S23

    General informationAll products were purchased either from Acros or Sigma Aldrich depending on their availability and were used without further purification. All solvents were purchased from Carlo Erba. Reactions were performed with an ultrasonic probe (Bioblock Scientific, Vibra cell 75042) and monitored by TLC (Kieselgel 60F254 MERCK aluminium sheet) with detection by UV light and/or phosphomolybdic acid solution and by HPLC (Shimazu). Flash column chromatography was performed on an automatic Grace apparatus, using 40 g connected silica gel cartridges. 1H and 13C NMR spectra were recorded on a 400 MHz Bruker UltraShield 400 MHz/54 mm Ultra long hold. Chemical shifts (δ) are quoted in ppm and are referenced to TMS as an internal standard. Coupling constants (J) are quoted in Hz. IR spectra were recorded on a Jasco FT/IR-4100 ATR.

    General procedure for the Barton decarboxylationIn a 100 mL Beaker containing a Brij®30 aqueous solution (300 mg in 30 mL), 2-mercaptopyridine-N-oxide (150 mg, 1.2 mmol), DCC (250 mg, 1.2 mmol), N-phenylmaleimide (268 mg, 1.5 mmol) and carboxylic acid (1.03 mmol) were introduced. The mixture was sonicated 20 min in an ice bath (the ultrasonic probe was placed at 1cm from the bottom of the beaker to ensure a homogenous dispersion). The crude mixture was lyophilized and the residue was purified on flash chromatography (Cyclohexane/EtOAc 1/0 to 7/3).

    General procedure for maleimide formationIn a 50 mL round bottom flask containing 1-phenylpyridin-2-ylthiopyrrolidine-2,5-dione (1 mmol) product in CH2Cl2 (10 mL) was added m-CPBA (246 mg, 10 mmol) and the mixture is stirred for 10 min. at 0°C. Then saturated NaHCO3 solution (30 mL) was added and the crude product extracted with CH2Cl2 (30 mL). After the evaporation of the solvent, toluene (20 mL) was added and the media was heated under reflux for 1h. Toluene was evaporated and the crude mixture was purified on flash chromatography (Cyclohexane/EtOAc 1/0 to 7/3).

    Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2015

    mailto:[email protected]

  • S2

    3-Pentyl-1-phenyl-4-(pyridin-2-ylthio)pyrrolidine-2,5-dione (1)

    NS

    O

    O

    N

    Following general procedure for Barton decarboxylation, white solid (218 mg, 60% yield).mp: 77-79°C1H NMR (400 MHz, CDCl3) δ ppm: 0.92 (t, J = 7.1 Hz, 3H, CH3), 1.34-1.37 (m, 4H, CH2), 1.53-1.60 (m, 2H, CH2), 1.78-1.87 (m, 1H, CH2), 2.04-2.12 (m, 1H, CH2), 3.23 (dt, J = 8.6 and 5.2 Hz, 1H, CHCO), 3.92 (d, J = 5.6 Hz, 1H, CHS), 7.02 (ddd, J = 7.4, 5.0 and 1.0 Hz, 1H, CH), 7.22 (d, J = 8.1 Hz, 1H, CH), 7.34-7.42 (m, 3H, CHar), 7.46-7.55 (m, 3H, CHar), 8.29 (ddd, J = 5.0, 1.8 and 1.0 Hz, 1H, CH)13C NMR (100 MHz, CDCl3) δ ppm: 14.0 (CH3), 22.4 (CH2), 26.1 (CH2), 30.7 (CH2), 31.6 (CH2), 46.9 (CH), 47.2 (CHS), 120.2 (CH), 122.1 (CH), 126.4 (2 CHPh), 128.5 (CHPh), 129.1 (2 CHPh), 132.5 (CPhN), 136.6 (CH), 149.0 (CHN), 156.1 (CS), 174.4 (COCHS), 177.4 (CO)νmax/cm-1: 1707 (C=O), 1389 (CH), 1173 (C-N),HRMS (ESI): found 355.1480; calculated 355.1480 for C20H23N2O2S

    3-Hexyl-1-phenyl-4-(pyridin-2-ylthio)pyrrolidine-2,5-dione (2)

    NS

    O

    O

    N

    Following general procedure for Barton decarboxylation, colourless wax (235 mg, 62% yield).1H NMR (400 MHz, CDCl3) δ ppm: 0.89 (t, J = 7.0 Hz, 3H, CH3), 1.26-1.39 (m, 6H, CH2), 1.55 (quin, J = 7.5 Hz, 2H, CH2), 1.77-1.87 (m, 1H, CH2), 2.04-2.13 (m, 1H, CH2), 3.24 (dt, J = 8.7 and 5.3 Hz, 1H, CHCO), 3.90 (d, J = 5.7 Hz, 1H, CHS), 7.01 (ddd, J = 7.4, 5.0 and 1.0 Hz, 1H, CH), 7.21 (d, J = 8.1 Hz, 1H, CH), 7.34-7.42 (m, 3H, CHar), 7.46-7.54 (m, 3H, CHar), 8.29 (ddd, J = 4.9, 1.7 and 0.9 Hz, 1H, CH)13C NMR (100 MHz, CDCl3) δ ppm: 14.0 (CH3), 22.5 (CH2), 26.4 (CH2), 29.1 (CH2), 30.7 (CH2), 31.5 (CH2), 46.9 (CH), 47.2 (CHS), 120.2 (CH), 122.1 (CH), 126.4 (2 CHPh), 128.5 (CHPh), 129.1 (2 CHPh), 132.5 (CPhN), 136.6 (CH), 148.9 (CHN), 156.0 (CS), 174.4 (COCHS), 177.3 (CO)νmax/cm-1: 1715 (C=O), 1381 (CH), 1183 (C-N),HRMS (ESI): found 369.1635; calculated 369.1632 for C21H25N2O2S

    3-Heptyl-1-phenyl-4-(pyridin-2-ylthio)pyrrolidine-2,5-dione (3)

    Following general procedure for Barton decarboxylation, colourless oil (228 mg, 58% yield).1H NMR (400 MHz, CDCl3) δ ppm: 0.88 (t, J = 6.9 Hz, 3H, CH3), 1.26-1.37 (m, 8H, CH2), 1.55 (quin, J = 7.5 Hz, 2H, CH2), 1.77-1.87 (m, 1H, CH2), 2.04-2.12 (m, 1H, CH2), 3.23 (dt, J = 8.7 and 5.2 Hz, 1H, CHCO), 3.93 (d, J = 5.6 Hz, 1H, CHS), 7.02 (ddd, J = 7.4, 5.0 and 1.0 Hz, 1H, CH), 7.23 (d, J = 8.1 Hz, 1H, CH), 7.33-7.41 (m, 3H, CHar), 7.45-7.55 (m, 3H, CHar), 8.29 (ddd, J = 5.0, 1.7 and 1.0 Hz, 1H, CH)13C NMR (100 MHz, CDCl3) δ ppm: 14.0 (CH3), 22.6 (CH2), 26.5 (CH2), 29.0 (CH2), 29.4 (CH2), 30.7 (CH2), 31.7 (CH2), 46.9 (CH), 47.1 (CHS), 120.3 (CH), 122.2 (CH), 126.4 (2 CHPh), 128.5 (CHPh), 129.1 (2 CHPh), 132.5 (CPhN), 136.7 (CH), 148.9 (CHN), 156.0 (CS), 174.4 (COCHS), 177.3 (CO)νmax/cm-1: 1715 (C=O), 1380 (CH), 1184 (C-N),HRMS (ESI): found 383.1788; calculated 383.1793 for C22H27N2O2S

    NS

    O

    O

    N

  • S3

    3-Nonyl-1-phenyl-4-(pyridin-2-ylthio)pyrrolidine-2,5-dione (4)

    Following general procedure for Barton decarboxylation, white solid (235 mg, 54% yield).mp: 56-57°C1H NMR (400 MHz, CDCl3) δ ppm: 0.88 (t, J = 6.9 Hz, 3H, CH3), 1.26-1.36 (m, 12H, CH2), 1.56 (quin, J = 7.4 Hz, 2H, CH2), 1.78-1.87 (m, 1H, CH2), 2.04-2.12 (m, 1H, CH2), 3.23 (dt, J = 8.8 and 5.1 Hz, 1H, CHCO), 3.92 (d, J = 5.6 Hz, 1H, CHS), 7.02 (dd, J = 6.7 and 5.0 Hz, 1H, CH), 7.23 (d, J = 8.1 Hz, 1H, CH), 7.35-7.41 (m, 3H, CHar), 7.46-7.55 (m, 3H, CHar), 8.29 (d, J = 4.5 Hz, 1H, CH)13C NMR (100 MHz, CDCl3) δ ppm: 14.1 (CH3), 22.6 (CH2), 26.5 (CH2), 29.2 (CH2), 29.3 (CH2), 29.4 (CH2), 29.5 (CH2), 30.8 (CH2), 31.8 (CH2), 46.9 (CH), 47.2 (CHS), 120.3 (CH), 122.2 (CH), 126.4 (2 CHPh), 128.5 (CHPh), 129.1 (2 CHPh), 132.5 (CPhN), 136.7 (CH), 149.0 (CHN), 156.0 (CS), 174.4 (COCHS), 177.3 (CO)νmax/cm-1: 1716 (C=O), 1386 (CH), 1180 (C-N),HRMS (ESI): found 411.2102; calculated 411.2106 for C24H31N2O2S

    1-Phenyl-3-(pyridin-2-ylthio)-4-undecylpyrrolidine-2,5-dione (5)

    Following general procedure for Barton decarboxylation, white solid (258 mg, 57% yield).mp: 62-65°C1H NMR (400 MHz, CDCl3) δ ppm: 0.88 (t, J = 6.9 Hz, 3H, CH3), 1.26 (bs, 16H, CH2), 1.55 (quin, J = 7.5 Hz, 2H, CH2), 1.77-1.87 (m, 1H, CH2), 2.03-2.12 (m, 1H, CH2), 3.23 (dt, J = 8.7 and 5.2 Hz, 1H, CHCO), 3.92 (d, J = 5.7 Hz, 1H, CHS), 7.01 (ddd, J = 7.4, 5.0 and 1.0 Hz, 1H, CH), 7.22 (dt, J = 8.1 and 0.9 Hz, 1H, CH), 7.34-7.41 (m, 3H, CHar), 7.45-7.54 (m, 3H, CHar), 8.28 (ddd, J = 5.0, 1.8 and 1.0 Hz, 1H, CH)13C NMR (100 MHz, CDCl3) δ ppm: 14.1 (CH3), 22.6 (CH2), 26.4 (CH2), 29.3 (CH2), 29.3 (CH2), 29.4 (CH2), 29.5 (CH2), 29.5 (2 CH2), 30.7 (CH2), 31.8 (CH2), 46.9 (CH), 47.1 (CHS), 120.2 (CH), 122.1 (CH), 126.4 (2 CHPh), 128.4 (CHPh), 129.0 (2 CHPh), 132.5 (CPhN), 136.6 (CH), 148.9 (CHN), 156.0 (CS), 174.3 (COCHS), 177.3 (CO)νmax/cm-1: 1714 (C=O), 1388 (CH), 1182 (C-N),HRMS (ESI): found 439.2418; calculated 439.2419 for C26H35N2O2S

    1-Phenyl-3-(pyridin-2-ylthio)-4-tetradecylpyrrolidine-2,5-dione (6)

    Following general procedure for Barton decarboxylation, white solid (301 mg, 61% yield).mp: 72-74°C1H NMR (400 MHz, CDCl3) δ ppm: 0.88 (t, J = 6.8 Hz, 3H, CH3), 1.26 (bs, 22H, CH2), 1.55 (quin, J = 7.5 Hz, 2H, CH2), 1.77-1.87 (m, 1H, CH2), 2.04-2.12 (m, 1H, CH2), 3.23 (dt, J = 8.7 and 5.1 Hz, 1H, CHCO), 3.91 (d, J = 5.6 Hz, 1H, CHS), 7.02 (dd, J = 6.7 and 5.6 Hz, 1H, CH), 7.22 (d, J = 8.1 Hz, 1H, CH), 7.35-7.41 (m, 3H, CHar), 7.46-7.55 (m, 3H, CHar), 8.29 (d, J = 4.9 Hz, 1H, CH)13C NMR (100 MHz, CDCl3) δ ppm: 14.1 (CH3), 22.7 (CH2), 26.5 (CH2), 29.3 (CH2), 29.3 (CH2), 29.4 (CH2), 29.5 (CH2), 29.6 (CH2), 29.6 (2 CH2), 29.7 (CH2), 29.7 (CH2), 30.8 (CH2), 31.9 (CH2), 46.9 (CH), 47.1 (CHS), 120.2 (CH), 122.1 (CH), 126.4 (2 CHPh), 128.4 (CHPh), 129.1 (2 CHPh), 132.5 (CPhN), 136.7 (CH), 148.9 (CHN), 156.0 (CS), 174.4 (COCHS), 177.3 (CO)νmax/cm-1: 1704 (C=O), 1391 (CH), 1174 (C-N),HRMS (ESI): found 481.2891; calculated 481.2889 for C29H41N2O2S

    NS

    O

    O

    N

    5

    NS

    O

    O

    N

    7

    NS

    O

    O

    N

    10

  • S4

    3-Pentadecyl-1-phenyl-4-(pyridin-2-ylthio)pyrrolidine-2,5-dione (7)

    Following general procedure for Barton decarboxylation, white solid (336 mg, 66% yield).mp: 68-71°C1H NMR (400 MHz, CDCl3) δ ppm: 0.80 (t, J = 6.9 Hz, 3H, CH3), 1.18-1.36 (m, 24H, CH2), 1.50 (quin, J = 7.4 Hz, 2H, CH2), 1.70-1.77 (m, 1H, CH2), 2.96-2.03 (m, 1H, CH2), 3.13 (dt, J = 8.8 and 5.1 Hz, 1H, CHCO), 3.86 (d, J = 5.6 Hz, 1H, CHS), 6.95 (dd, J = 6.7 and 5.0 Hz, 1H, CH), 7.17 (d, J = 8.1 Hz, 1H, CH), 7.27-7.34 (m, 3H, CHar), 7.39-7.49 (m, 3H, CHar), 8.22 (d, J = 4.5 Hz, 1H, CH)13C NMR (100 MHz, CDCl3) δ ppm: 14.1 (CH3), 22.7 (CH2), 26.5 (CH2), 29.4 (CH2), 29.4 (CH2), 29.5 (CH2), 29.6 (CH2), 29.6 (CH2), 29.6 (CH2), 29.7 (CH2), 30.7 (CH2), 31.9 (CH2), 46.9 (CH), 47.2 (CHS), 120.3 (CH), 122.2 (CH), 126.4 (2 CHPh), 128.5 (CHPh), 129.1 (2 CHPh), 132.5 (CPhN), 136.8 (CH), 148.9 (CHN), 156.0 (CS), 174.4 (COCHS), 177.3 (CO)νmax/cm-1: 1708 (C=O), 1387 (CH), 1173 (C-N),HRMS (ESI): found 495.3047; calculated 495.3045 for C30H43N2O2S

    3-Heptadecyl-1-phenyl-4-(pyridin-2-ylthio)pyrrolidine-2,5-dione (8)

    Following general procedure for Barton decarboxylation, white solid (296 mg, 55% yield).mp: 85-86°C1H NMR (400 MHz, CDCl3) δ ppm: 0.88 (t, J = 6.9 Hz, 3H, CH3), 1.26 (bs, 28H, CH2), 1.56 (quin, J = 7.5 Hz, 2H, CH2), 1.78-1.87 (m, 1H, CH2), 2.04-2.13 (m, 1H, CH2), 3.23 (dt, J = 8.7 and 5.2 Hz, 1H, CHCO), 3.95 (d, J = 5.6 Hz, 1H, CHS), 7.03 (ddd, J = 7.4, 5.0 and 1.0 Hz, 1H, CH), 7.24 (dt, J = 8.1 and 0.9 Hz, 1H, CH), 7.34-7.42 (m, 3H, CHar), 7.46-7.56 (m, 3H, CHar), 8.30 (ddd, J = 5.0, 1.8 and 1.0 Hz, 1H, CH)13C NMR (100 MHz, CDCl3) δ ppm: 14.1 (CH3), 22.7 (CH2), 26.5 (CH2), 29.3 (CH2), 29.3 (CH2), 29.4 (CH2), 29.5 (CH2), 29.6 (CH2), 29.7 (2 CH2), 29.7 (5 CH2), 30.8 (CH2), 31.9 (CH2), 46.9 (CH), 47.2 (CHS), 120.3 (CH), 122.3 (CH), 126.4 (2 CHPh), 128.5 (CHPh), 129.1 (2 CHPh), 132.5 (CPhN), 136.8 (CH), 148.9 (CHN), 156.0 (CS), 174.4 (COCHS), 177.3 (CO)νmax/cm-1: 1708 (C=O), 1388 (CH), 1169 (C-N),HRMS (ESI): found 523.3363; calculated 523.3359 for C32H47N2O2S and found 545.3198; calculated 545.3177 for C32H46N2O2SNa

    (Z)-3-(Heptadec-8-en-1-yl)-1-phenyl-4-(pyridin-2-ylthio)pyrrolidine-2,5-dione (9)

    Following general procedure for Barton decarboxylation, colourless oil (321 mg, 60% yield).1H NMR (400 MHz, CDCl3) δ ppm: 0.88 (t, J = 6.9 Hz, 3H, CH3), 1.27-1.31 (m, 22H, CH2), 1.56 (quin, J = 7.4 Hz, 2H, CH2), 1.77-1.87 (m, 1H, CH2), 2.01-2.05 (m, 1H, CH2), 3.23 (dt, J = 8.7 and 5.2 Hz, 1H, CHCO), 3.91 (d, J = 5.7 Hz, 1H, CHS), 5.35 (dt, J = 5.7 and 3.5 Hz, 2H, CH), 7.01 (ddd, J = 7.4, 5.0 and 1.0 Hz, 1H, CH), 7.23 (dt, J = 8.1 and 0.9 Hz, 1H, CH), 7.35-7.41 (m, 3H, CHar), 7.46-7.55 (m, 3H, CHar), 8.29 (ddd, J = 4.9, 1.8 and 0.9 Hz, 1H, CH)13C NMR (100 MHz, CDCl3) δ ppm: 14.1 (CH3), 22.7 (CH2), 26.5 (CH2), 27.1 (CH2), 27.2 (CH2), 29.1 (CH2), 29.2 (CH2), 29.3 (2 CH2), 29.4 (CH2), 29.5 (CH2), 29.7 (CH2), 29.7 (CH2), 30.7 (CH2), 31.9 (CH2), 46.9 (CH), 47.1 (CHS), 120.2 (CH), 122.1 (CH), 126.4 (2 CHPh), 128.4 (CHPh), 129.1 (2 CHPh), 129.7 (CH), 130.0 (CH), 132.5 (CPhN), 136.6 (CH), 149.0 (CHN), 156.0 (CS), 174.3 (COCHS), 177.3 (CO)νmax/cm-1: 1717 (C=O), 1384 (CH), 1179 (C-N),HRMS (ESI): found 521.3221; calculated 521.3202 for C32H45N2O2S

    NS

    O

    O

    N

    11

    NS

    O

    O

    N

    13

    NS

    O

    O

    N

    5

    5

  • S5

    3-((8Z,11Z)-Heptadeca-8,11-dien-1-yl)-1-phenyl-4-(pyridin-2-ylthio)pyrrolidine-2,5-dione (10)

    Following general procedure for Barton decarboxylation, colourless oil (327 mg, 61% yield).1H NMR (400 MHz, CDCl3) δ ppm: 0.89 (t, J = 7.0 Hz, 3H, CH3), 1.29-1.37 (m, 14H, CH2), 1.55 (quin, J = 7.2 Hz, 2H, CH2), 1.76-1.86 (m, 1H, CH2), 2.06 (q, J = 6.8 Hz, 5H, CH2), 2.78 (t, J = 6.3 Hz, 2H, CH2), 3.23 (dt, J = 8.7 and 5.2 Hz, 1H, CHCO), 3.89 (d, J = 5.7 Hz, 1H, CHS), 5.30-5.43 (m, 4H, CH), 6.98 (ddd, J = 7.3, 5.0 and 0.8 Hz, 1H, CH), 7.19 (d, J = 8.1 Hz, 1H, CH), 7.34-7.40 (m, 3H, CHar), 7.44-7.52 (m, 3H, CHar), 8.27 (ddd, J = 4.9, 1.7 and 1.0 Hz, 1H, CH)13C NMR (100 MHz, CDCl3) δ ppm: 14.0 (CH3), 22.4 (CH2), 25.5 (CH2), 26.4 (CH2), 27.1 (2 CH2), 29.0 (CH2), 29.1 (CH2), 29.2 (CH2), 29.3 (CH2), 29.5 (CH2), 30.6 (CH2), 31.4 (CH2), 46.8 (CH), 47.0 (CHS), 120.1 (CH), 121.9 (CH), 126.3 (2 CHPh), 127.8 (CH), 127.9 (CH), 128.3 (CHPh), 128.9 (2 CHPh), 129.9 (CH), 130.1 (CH), 132.5 (CPhN), 136.5 (CH), 148.9 (CHN), 155.9 (CS), 174.2 (COCHS), 177.2 (CO)νmax/cm-1: 1717 (C=O), 1382 (CH), 1179 (C-N),HRMS (ESI): found 519.3052; calculated 519.3046 for C32H43N2O2S

    3-Pentyl-1-phenyl-1H-pyrrole-2,5-dione (11)

    Following general procedure for maleimide formation, white solid, (242 mg, quantitative yield).mp: 72-73°C1H NMR (400 MHz, CDCl3) δ ppm: 0.93 (t, J = 7.1 Hz, 3H, CH3), 1.33-1.42 (m, 4H, CH2), 1.63-1.70 (m, 2H, CH2), 2.52 (dt, J = 7.7 and 1.7 Hz, 2H, CH2), 6.43 (t, J = 1.2 Hz, 1H, CH), 7.33-7.36 (m, 3H, CHar), 7.43-7.48 (m, 2H, CHar)13C NMR (100 MHz, CDCl3) δ ppm: 13.9 (CH3), 22.3 (CH2), 25.5 (CH2), 26.8 (CH2), 31.3 (CH2), 125.9 (2 CHPh), 126.3 (CHCO), 127.6 (CHPh), 129.0 (2 CHPh), 131.6 (CPhN), 150.4 (COCCH2), 169.7 (CO), 170.4 (COCCH2)νmax/cm-1: 1707 (C=O), 1388 (CH), 1179 (C-N)HRMS (ESI): found 244.1340, calculated 244.1338 for C15H18NO2

    NS

    O

    O

    N

    5

    4

    O

    O

    N

  • S6

    3,4-Dipentyl-1-phenyl-3-(pyridin-2-ylthio)pyrrolidine-2,5-dione ((±)12a and (±)12b)

    In a 100 mL Beaker containing a Brij®30 aqueous solution (300 mg in 30 mL), 2-mercaptopyridine-N-oxide (225 mg, 1.8 mmol), DCC (375 mg, 1.8 mmol), 11 (243 mg, 1 mmol) and caproic acid (174 mg,1.5 mmol) were introduced. The mixture was sonicated 20 min in an ice bath (the ultrasonic probe was placed at 1cm from the bottom of the beaker to ensure a homogenous dispersion). The crude mixture was lyophilized and the residue was purified on flash chromatography (Cyclohexane/EtOAc 1/0 to 7/3).Pale yellow oil (200 mg, 47% yield).1H NMR (400 MHz, CDCl3) δ ppm: 0.85-0.93 (m, 6H, CH3), 1.27-1.38 (m, 9H, CH2), 1.56-1.77 (m, 4H, CH2), 1.82-2.16 (m, 3H, CH2), 2.96 (dd, J = 7.1 and 5.7 Hz, 0.6H, CH), 3.65 (t, J = 6.8 Hz, 0.4H, CH), 6.99 (ddd, J = 7.4, 6.2, and 5.0 Hz, 1H, CH), 7.17-7.22 (m, 1H, CH), 7.26-7.29 (m, 1H, CH), 7.32-7.52 (m, 5H, CHPh), 8.19 (ddd, J = 5.0, 1.8 and 0.9 Hz, 0.6H, CH), 8.30 (ddd, J = 5.0, 1.8 and 0.9 Hz, 0.4H, CH)13C NMR (100 MHz, CDCl3) δ ppm: 13.9 (CH3), 14.0 (CH3), 22.2 (CH2), 22.3 (CH2), 22.3 (CH2), 22.3 (CH2), 24.0 (CH2), 24.3 (CH2), 28.0 (CH2), 28.1 (CH2), 28.7 (CH2), 31.7 (2 CH2), 31.7 (CH2), 31.8 (CH2), 33.9 (CH2CH), 38.4 (CH2CS), 47.8 (CHCO), 48.1 (CHCO), 56.9 (CSCO), 59.0 (CSCO), 120.0 (CH), 120.2 (CH), 122.0 (CH), 122.1 (CH), 126.3 (2 CHPh), 126.4 (2 CHPh), 128.1 (CHPh), 128.3 (CHPh), 128.9 (2 CHPh), 129.0 (2 CHPh), 132.6 (CPhN), 136.4 (CH), 136.4 (CH), 148.7 (CHN), 148.9 (CHN), 156.9 (CS), 157.4 (CS), 176.2 (COCS), 176.9 (COCS), 177.1 (COCH), 177.5 (COCH)νmax/cm-1: 1714 (C=O), 1387 (CH), 1182 (C-N),HRMS (ESI): found 447.2086, calculated 447.2082 for C25H32N2O2SNa

    3,4-Dipentyl-1-phenyl-1H-pyrrole-2,5-dione (13)

    Following general procedure for maleimide formation, pale yellow oil (310 mg, quantitative yield).1H NMR (400 MHz, CDCl3) δ ppm: 0.92 (t, J = 7.1 Hz, 6H, CH3), 1.34-1.39 (m, 8H, CH2), 1.58-1.61 (m, 4H, CH2), 2.46 (t, J = 7.7 Hz, 4H, CH2), 7.31-7.38 (m, 3H, CHar), 7.42-7.46 (m, 2H, CHar)13C NMR (100 MHz, CDCl3) δ ppm: 13.9 (CH3), 22.4 (CH2), 23.8 (CH2), 28.3 (CH2), 31.8 (CH2), 125.7 (2 CHPh), 127.2 (CHPh), 129.0 (2 CHPh), 132.0 (CPhN), 141.2 (C=C), 170.8 (CO)νmax/cm-1: 1709 (C=O), 1305 (CH), 1198 (C-N)HRMS (ESI): found 314.2120, calculated 314.2106 for C20H28NO2

    CC

    N

    O

    O

    CC

    N

    O

    OH H

    S S

    N N

    (±)12a (±)12b

    N

    O

    O

  • S7

    ppm (t1)102030405060708090100110120130140150160170180190

    177.

    363

    174.

    395

    156.

    040

    149.

    013

    136.

    625

    132.

    526

    129.

    091

    128.

    467

    126.

    403

    122.

    079

    120.

    226

    77.3

    1777

    .202

    77.0

    0076

    .682

    47.1

    8246

    .905

    31.5

    9730

    .709

    26.1

    4922

    .403

    13.9

    76

    NS

    O

    O

    N

    3-pentyl-1-phenyl-4-(pyridin-2-ylthio)pyrrolidine-2,5-dione (1)

    ppm (t1)1.02.03.04.05.06.07.08.09.0

    8.30

    18.

    298

    8.29

    68.

    294

    8.28

    88.

    286

    8.28

    48.

    282

    7.55

    47.

    550

    7.53

    47.

    531

    7.51

    57.

    511

    7.50

    07.

    482

    7.46

    77.

    463

    7.45

    77.

    415

    7.41

    27.

    409

    7.39

    37.

    367

    7.36

    47.

    346

    7.34

    37.

    236

    7.21

    67.

    037

    7.03

    57.

    025

    7.02

    27.

    019

    7.01

    67.

    006

    7.00

    4

    3.93

    33.

    918

    3.25

    73.

    244

    3.23

    63.

    231

    3.22

    23.

    209

    2.12

    42.

    111

    2.10

    32.

    090

    2.07

    02.

    065

    2.05

    32.

    048

    2.03

    5

    1.87

    11.

    854

    1.84

    91.

    832

    1.81

    71.

    811

    1.79

    71.

    776

    1.59

    91.

    582

    1.57

    51.

    564

    1.54

    61.

    525

    1.36

    81.

    360

    1.35

    01.

    342

    0.92

    00.

    902

    0.88

    4

    1.00

    3.063.001.011.02

    3.15

    4.002.15

    1.19

    1.09

    1.02

    1.01

    NS

    O

    O

    N

  • S8

    ppm (t2)3.003.103.203.303.403.503.603.703.803.904.00

    8.00

    8.10

    8.20

    8.30

    8.40

    8.50

    8.60

    8.70

    ppm (t1)

    NOESY

  • S9

    ppm (t1)1.02.03.04.05.06.07.08.09.0

    8.29

    28.

    281

    7.54

    67.

    542

    7.52

    67.

    523

    7.50

    87.

    503

    7.49

    67.

    482

    7.46

    77.

    463

    7.45

    77.

    412

    7.40

    97.

    393

    7.37

    57.

    368

    7.36

    47.

    347

    7.26

    07.

    228

    7.20

    87.

    029

    7.01

    47.

    011

    7.00

    86.

    998

    6.99

    6

    6.84

    73.

    908

    3.89

    43.

    260

    3.24

    73.

    238

    3.23

    33.

    225

    3.21

    1

    2.12

    52.

    112

    2.10

    42.

    091

    2.08

    42.

    078

    2.07

    12.

    067

    2.06

    22.

    054

    2.04

    92.

    043

    2.03

    7

    1.86

    91.

    852

    1.84

    71.

    830

    1.81

    51.

    809

    1.79

    41.

    774

    1.57

    31.

    554

    1.53

    61.

    515

    1.31

    81.

    311

    1.30

    10.

    904

    0.88

    60.

    868

    1.00

    3.293.220.981.030.12

    3.31

    6.22

    2.23

    1.19

    1.04

    1.01

    1.04

    NS

    O

    O

    N

    ppm (t1)102030405060708090100110120130140150160170180190

    177.

    338

    174.

    370

    156.

    017

    148.

    983

    136.

    619

    134.

    159

    132.

    518

    129.

    069

    128.

    445

    126.

    392

    122.

    070

    120.

    213

    77.3

    1877

    .000

    76.6

    82

    47.1

    4946

    .891

    31.5

    2630

    .727

    29.0

    6926

    .423

    22.5

    02

    14.0

    11

    NS

    O

    O

    N

    3-hexyl-1-phenyl-4-(pyridin-2-ylthio)pyrrolidine-2,5-dione (2)

  • S10

    ppm (t1)102030405060708090100110120130140150160170180190

    177.

    317

    174.

    372

    155.

    973

    148.

    908

    136.

    709

    134.

    158

    132.

    498

    129.

    069

    128.

    452

    126.

    390

    126.

    024

    122.

    151

    120.

    257

    77.3

    1877

    .000

    76.6

    82

    47.1

    3346

    .893

    31.6

    8530

    .718

    29.3

    6729

    .003

    26.4

    7322

    .569

    14.0

    44

    SN

    O

    O

    N

    ppm (t1)1.02.03.04.05.06.07.08.09.0

    8.30

    08.

    296

    8.28

    88.

    285

    7.55

    37.

    548

    7.53

    37.

    530

    7.51

    47.

    510

    7.49

    97.

    481

    7.47

    17.

    466

    7.46

    27.

    411

    7.39

    27.

    373

    7.36

    67.

    363

    7.35

    77.

    349

    7.34

    57.

    260

    7.23

    57.

    215

    7.03

    67.

    024

    7.01

    87.

    015

    7.00

    57.

    003

    6.84

    63.

    934

    3.92

    0

    3.25

    43.

    241

    3.23

    23.

    227

    3.21

    93.

    206

    2.12

    42.

    112

    2.10

    32.

    090

    2.08

    32.

    077

    2.07

    02.

    066

    2.06

    02.

    053

    2.04

    82.

    036

    1.84

    71.

    830

    1.81

    51.

    809

    1.79

    41.

    576

    1.55

    71.

    538

    1.28

    91.

    281

    1.27

    81.

    265

    1.25

    60.

    898

    0.88

    10.

    864

    1.00

    3.473.480.981.010.32

    1.02

    1.02

    1.17

    1.52

    2.56

    8.16

    3.45

    SN

    O

    O

    N

    3-heptyl-1-phenyl-4-(pyridin-2-ylthio)pyrrolidine-2,5-dione (3)

  • S11

  • S12

    ppm (t1)102030405060708090100110120130140150160170180190

    177.

    340

    174.

    386

    156.

    010

    148.

    967

    136.

    695

    132.

    515

    129.

    086

    128.

    467

    126.

    409

    122.

    148

    120.

    260

    77.3

    1877

    .000

    76.6

    82

    47.1

    5446

    .931

    31.8

    3330

    .747

    29.4

    5829

    .420

    29.3

    5229

    .236

    26.4

    8822

    .653

    14.0

    98

    SN

    O

    O

    N

    5

    ppm (t1)1.02.03.04.05.06.07.08.09.0

    8.29

    68.

    285

    7.55

    47.

    550

    7.53

    47.

    531

    7.51

    57.

    511

    7.50

    17.

    483

    7.46

    37.

    412

    7.39

    97.

    394

    7.38

    97.

    375

    7.36

    67.

    363

    7.34

    57.

    260

    7.23

    57.

    215

    7.03

    57.

    023

    7.01

    97.

    006

    6.85

    3

    3.92

    53.

    911

    3.24

    33.

    234

    3.23

    13.

    222

    2.10

    32.

    091

    2.08

    32.

    077

    2.07

    12.

    067

    2.05

    42.

    049

    1.84

    81.

    831

    1.81

    61.

    795

    1.77

    51.

    573

    1.55

    51.

    537

    1.26

    40.

    897

    0.88

    00.

    863

    1.00

    3.003.041.081.050.02

    3.30

    12.70

    2.18

    1.46

    1.07

    1.00

    1.00

    SN

    O

    O

    N

    5

    3-nonyl-1-phenyl-4-(pyridin-2-ylthio)pyrrolidine-2,5-dione (4)

  • S13

    ppm (t1)102030405060708090100110120130140150160170180190

    177.

    291

    174.

    340

    155.

    963

    148.

    897

    136.

    642

    132.

    485

    129.

    029

    128.

    408

    126.

    365

    122.

    080

    120.

    203

    77.3

    1877

    .000

    76.6

    82

    47.1

    0446

    .856

    31.8

    4230

    .684

    29.5

    3629

    .458

    29.3

    7829

    .309

    29.2

    7626

    .444

    22.6

    2414

    .072

    NS

    O

    O7

    N

    ppm (t1)1.02.03.04.05.06.07.08.09.0

    8.29

    48.

    292

    8.29

    08.

    287

    8.28

    28.

    279

    8.27

    78.

    275

    7.54

    17.

    537

    7.52

    27.

    521

    7.51

    87.

    502

    7.49

    87.

    492

    7.47

    87.

    475

    7.46

    37.

    459

    7.45

    37.

    411

    7.40

    77.

    404

    7.38

    97.

    368

    7.36

    47.

    346

    7.34

    4

    7.26

    07.

    227

    7.22

    57.

    223

    7.20

    77.

    205

    7.20

    27.

    025

    7.02

    37.

    013

    7.01

    07.

    007

    7.00

    46.

    994

    6.99

    23.

    923

    3.90

    9

    3.25

    43.

    241

    3.23

    23.

    228

    3.21

    93.

    206

    2.12

    12.

    100

    2.08

    72.

    080

    2.07

    42.

    068

    2.06

    32.

    058

    2.05

    12.

    046

    2.03

    31.

    866

    1.84

    81.

    844

    1.82

    71.

    812

    1.80

    61.

    791

    1.77

    11.

    589

    1.57

    21.

    553

    1.53

    51.

    514

    1.26

    20.

    900

    0.88

    30.

    866

    1.00

    3.353.171.041.09

    1.14

    1.11

    1.17

    1.42

    2.41

    16.25

    3.56

    NS

    O

    O7

    N

    1-phenyl-3-(pyridin-2-ylthio)-4-undecylpyrrolidine-2,5-dione (5)

  • S14

    ppm (t1)1.02.03.04.05.06.07.08.09.0

    8.29

    48.

    281

    7.54

    67.

    527

    7.50

    07.

    482

    7.46

    67.

    462

    7.41

    17.

    408

    7.39

    27.

    374

    7.36

    87.

    365

    7.35

    97.

    347

    7.26

    07.

    231

    7.21

    07.

    031

    7.01

    77.

    014

    7.00

    03.

    919

    3.90

    63.

    256

    3.24

    33.

    234

    3.22

    93.

    221

    3.20

    8

    2.12

    42.

    111

    2.10

    32.

    090

    2.08

    22.

    077

    2.07

    02.

    066

    2.06

    02.

    053

    2.04

    82.

    036

    1.86

    71.

    850

    1.84

    61.

    829

    1.81

    31.

    807

    1.79

    31.

    773

    1.58

    91.

    572

    1.55

    41.

    535

    1.51

    41.

    259

    0.89

    80.

    881

    0.86

    4

    3.20

    22.032.17

    1.29

    1.11

    1.00

    1.00

    1.00

    3.093.000.971.01

    NS

    O

    O10

    N

    1-phenyl-3-(pyridin-2-ylthio)-4-tetradecylpyrrolidine-2,5-dione (6)

  • S15

    ppm (t1)102030405060708090100110120130140150160170180190

    177.

    319

    174.

    361

    155.

    994

    148.

    933

    136.

    661

    132.

    504

    129.

    063

    128.

    440

    126.

    384

    122.

    105

    120.

    228

    77.3

    1877

    .000

    76.6

    82

    47.1

    3146

    .884

    31.8

    8830

    .722

    29.6

    5129

    .618

    29.5

    7129

    .495

    29.4

    1229

    .328

    26.4

    7322

    .660

    14.1

    03

    NS

    O

    O10

    N

  • S16

    ppm (t1)1.02.03.04.05.06.07.08.09.0

    8.22

    98.

    227

    8.21

    87.

    489

    7.48

    57.

    469

    7.46

    67.

    451

    7.44

    67.

    430

    7.42

    67.

    412

    7.39

    77.

    393

    7.34

    57.

    342

    7.33

    97.

    329

    7.32

    37.

    318

    7.30

    57.

    302

    7.29

    67.

    292

    7.28

    77.

    274

    7.19

    07.

    170

    7.15

    0

    6.97

    36.

    970

    6.96

    06.

    958

    6.95

    46.

    942

    3.87

    13.

    857

    3.18

    23.

    169

    3.16

    13.

    156

    3.14

    73.

    134

    2.03

    42.

    021

    2.01

    32.

    008

    2.00

    11.

    997

    1.99

    11.

    984

    1.97

    91.

    967

    1.80

    01.

    778

    1.76

    11.

    746

    1.74

    01.

    725

    1.70

    51.

    520

    1.50

    31.

    485

    1.46

    61.

    445

    1.18

    50.

    826

    0.80

    90.

    792

    1.00

    1.08

    6.251.12

    1.05

    1.02

    4.06

    2.27

    1.48

    1.00

    28.91

    NS

    O

    O11

    N

    ppm (t1)102030405060708090100110120130140150160170180190

    177.

    371

    174.

    428

    156.

    035

    148.

    950

    136.

    806

    132.

    558

    129.

    141

    128.

    522

    126.

    451

    122.

    251

    120.

    337

    77.3

    7177

    .257

    77.0

    5476

    .736

    47.1

    9546

    .964

    31.9

    6030

    .793

    29.7

    2829

    .692

    29.6

    4529

    .568

    29.4

    8529

    .414

    29.4

    0026

    .545

    22.7

    3114

    .170

    NS

    O

    O11

    N

    3-pentadecyl-1-phenyl-4-(pyridin-2-ylthio)pyrrolidine-2,5-dione (7)

  • S17

    ppm (t1)1.02.03.04.05.06.07.08.09.0

    8.30

    78.

    305

    8.30

    38.

    300

    8.29

    58.

    292

    8.29

    08.

    288

    7.56

    47.

    560

    7.54

    47.

    541

    7.52

    67.

    521

    7.50

    17.

    483

    7.46

    37.

    458

    7.41

    67.

    413

    7.40

    97.

    399

    7.39

    47.

    389

    7.37

    97.

    376

    7.36

    67.

    362

    7.35

    77.

    344

    7.34

    2

    7.26

    07.

    248

    7.24

    67.

    243

    7.22

    87.

    225

    7.22

    37.

    048

    7.04

    57.

    035

    7.03

    37.

    029

    7.02

    77.

    017

    7.01

    4

    3.95

    53.

    941

    3.25

    13.

    238

    3.22

    93.

    224

    3.21

    63.

    203

    2.12

    62.

    113

    2.10

    52.

    092

    2.08

    52.

    079

    2.07

    22.

    068

    2.06

    22.

    055

    2.05

    02.

    038

    1.87

    21.

    854

    1.85

    01.

    833

    1.81

    81.

    812

    1.79

    71.

    777

    1.59

    21.

    575

    1.55

    61.

    538

    1.51

    71.

    256

    0.89

    60.

    879

    0.86

    2

    1.00

    1.031.053.08

    3.24

    1.03

    1.07

    1.20

    1.35

    2.3828.19

    3.20

    NS

    O

    O13

    N

    ppm (t1)102030405060708090100110120130140150160170180190

    177.

    304

    174.

    369

    155.

    974

    148.

    870

    136.

    800

    132.

    508

    129.

    093

    128.

    476

    126.

    404

    122.

    249

    120.

    312

    77.3

    1777

    .000

    76.6

    83

    47.1

    4946

    .926

    31.9

    1430

    .746

    29.6

    9129

    .647

    29.6

    0029

    .524

    29.4

    3829

    .369

    29.3

    5326

    .500

    22.6

    8314

    .119

    NS

    O

    O13

    N

    3-heptadecyl-1-phenyl-4-(pyridin-2-ylthio)pyrrolidine-2,5-dione (8)

  • S18

    ppm (t1)1.02.03.04.05.06.07.08.09.0

    8.29

    68.

    294

    8.29

    28.

    289

    8.28

    48.

    281

    8.27

    98.

    277

    7.54

    67.

    541

    7.52

    67.

    521

    7.50

    77.

    502

    7.48

    27.

    466

    7.46

    27.

    457

    7.41

    47.

    411

    7.40

    87.

    392

    7.36

    97.

    365

    7.36

    07.

    348

    7.34

    57.

    260

    7.23

    07.

    228

    7.22

    67.

    210

    7.20

    77.

    205

    7.02

    97.

    027

    7.01

    77.

    014

    7.01

    17.

    008

    6.99

    86.

    996

    6.84

    35.

    366

    5.35

    75.

    352

    5.34

    95.

    343

    5.33

    4

    3.91

    13.

    897

    3.25

    83.

    245

    3.23

    63.

    232

    3.22

    33.

    210

    2.05

    32.

    049

    2.03

    62.

    023

    2.00

    91.

    866

    1.84

    91.

    845

    1.82

    81.

    813

    1.80

    61.

    792

    1.77

    21.

    593

    1.57

    71.

    558

    1.54

    01.

    519

    1.31

    21.

    308

    1.26

    90.

    896

    0.88

    00.

    862

    1.00

    3.173.111.011.050.04

    2.03

    1.02

    1.02

    4.451.43

    2.45

    22.25

    3.32

    NS

    O

    O5

    N

    5

    ppm (t1)102030405060708090100110120130140150160170180190

    177.

    294

    174.

    332

    156.

    003

    148.

    955

    136.

    627

    132.

    508

    129.

    960

    129.

    689

    129.

    054

    128.

    431

    126.

    377

    122.

    075

    120.

    211

    77.3

    1877

    .000

    76.6

    82

    47.1

    2946

    .888

    31.8

    6030

    .723

    29.7

    2629

    .656

    29.4

    8229

    .385

    29.2

    7929

    .245

    29.1

    3427

    .186

    27.1

    3226

    .470

    22.6

    4514

    .090

    NS

    O

    O5

    N

    5

    (Z)-3-(heptadec-8-en-1-yl)-1-phenyl-4-(pyridin-2-ylthio)pyrrolidine-2,5-dione (9)

  • S19

    ppm (t1)1.02.03.04.05.06.07.08.09.0

    8.27

    88.

    276

    8.27

    48.

    272

    8.26

    68.

    264

    8.26

    28.

    259

    7.51

    57.

    511

    7.49

    57.

    490

    7.48

    37.

    469

    7.45

    07.

    444

    7.40

    07.

    397

    7.39

    47.

    378

    7.36

    97.

    365

    7.36

    07.

    348

    7.34

    57.

    339

    7.26

    07.

    203

    7.18

    27.

    000

    6.99

    86.

    988

    6.98

    66.

    982

    6.98

    06.

    969

    6.96

    75.

    425

    5.39

    45.

    377

    5.36

    75.

    362

    5.35

    25.

    347

    5.30

    03.

    898

    3.88

    43.

    252

    3.23

    93.

    230

    3.22

    53.

    216

    3.20

    3

    2.79

    72.

    781

    2.76

    62.

    081

    2.06

    42.

    047

    2.03

    01.

    856

    1.83

    91.

    834

    1.81

    81.

    813

    1.80

    21.

    796

    1.78

    11.

    762

    1.58

    61.

    572

    1.55

    31.

    535

    1.51

    51.

    370

    1.34

    01.

    326

    1.32

    31.

    313

    1.30

    81.

    302

    1.28

    71.

    285

    0.90

    50.

    888

    0.87

    0

    1.00

    3.092.970.961.00

    4.42

    1.07

    1.02

    2.21

    5.30

    1.61

    2.1214.01

    3.20

    NS

    O

    O5

    N

    4

    ppm (t1)102030405060708090100110120130140150160170180190

    177.

    172

    174.

    206

    155.

    917

    148.

    857

    136.

    492

    132.

    446

    130.

    046

    129.

    865

    128.

    924

    128.

    293

    127.

    900

    127.

    751

    126.

    289

    121.

    913

    120.

    077

    77.3

    1877

    .000

    76.6

    82

    47.0

    0946

    .776

    31.3

    7130

    .595

    29.4

    5629

    .273

    29.1

    9929

    .139

    29.0

    2927

    .062

    26.3

    7625

    .507

    22.4

    35

    13.9

    65

    NS

    O

    O5

    N

    4

    3-((8Z,11Z)-heptadeca-8,11-dien-1-yl)-1-phenyl-4-(pyridin-2-ylthio)pyrrolidine-2,5-dione (10)

  • S20

    ppm (t1)1.02.03.04.05.06.07.08.09.0

    7.40

    47.

    385

    7.37

    97.

    365

    7.29

    27.

    286

    7.28

    37.

    278

    7.27

    57.

    269

    7.26

    57.

    262

    7.25

    7

    7.18

    9

    6.36

    26.

    357

    6.35

    2

    2.46

    52.

    460

    2.44

    62.

    442

    2.42

    62.

    422

    1.61

    01.

    591

    1.57

    2

    1.33

    11.

    322

    1.31

    31.

    304

    1.29

    8

    0.87

    40.

    865

    0.85

    70.

    851

    0.84

    40.

    839

    3.30

    4.35

    2.18

    2.19

    1.00

    2.123.07

    N

    O

    O

    ppm (t1)102030405060708090100110120130140150160170180190

    170.

    424

    169.

    734

    150.

    351

    131.

    610

    129.

    024

    127.

    627

    126.

    306

    125.

    897

    77.3

    1877

    .203

    77.0

    0076

    .683

    31.3

    3726

    .758

    25.4

    6022

    .300

    13.9

    01

    N

    O

    O

    3-pentyl-1-phenyl-1H-pyrrole-2,5-dione (11)

  • S21

    ppm (t1)1.02.03.04.05.06.07.08.09.0

    8.3118.3098.2998.2968.2078.1968.1947.5207.5157.5007.4787.4657.4617.4547.4527.4487.4347.4187.4147.4017.3987.3847.3797.3677.3637.3537.3487.3427.3337.3297.3187.2857.2817.2767.2607.2187.1977.1887.1687.0107.0076.9946.9916.9796.9766.9633.6743.6573.640

    2.9812.9672.9642.9492.1592.1492.1252.1142.0952.0842.0592.0482.0432.0382.0332.0162.0132.0092.0051.9961.9871.9821.9741.9691.9631.9591.9491.8971.8871.8671.8631.8571.8521.8341.8231.7661.7531.7471.7401.7351.7271.7211.7091.7031.6941.6861.6811.6741.6631.6571.6491.6411.6321.6201.6061.6021.5891.5761.5581.5381.5331.4261.3791.3701.3611.3521.3431.3391.3301.3201.3101.3011.2921.2831.2740.9260.9090.9050.8950.8870.8780.8690.8600.852

    5.15

    1.07

    1.01

    1.00

    0.44

    0.55

    0.44

    0.61

    6.45

    8.89

    3.99

    3.23

    CC N

    O

    O

    CC N

    O

    O

    S SN N

    3,4-dipentyl-1-phenyl-3-(pyridin-2-ylthio)pyrrolidine-2,5-dione (12a and 12b)

  • S22

    ppm (t1)102030405060708090100110120130140150

    148.

    719

    148.

    478

    136.

    245

    136.

    214

    128.

    803

    128.

    652

    128.

    093

    127.

    925

    126.

    182

    126.

    066

    121.

    906

    120.

    023

    119.

    813

    47.9

    4947

    .667

    38.1

    3833

    .667

    31.5

    7931

    .512

    31.4

    8028

    .577

    27.9

    0627

    .687

    24.1

    0023

    .693

    22.1

    3822

    .092

    22.0

    7022

    .017

    13.7

    6213

    .688

    13.6

    63

    ppm (t1)102030405060708090100110120130140150160170180190

    177.524177.104176.857176.171

    157.431156.936148.922148.686

    136.440136.404132.637132.519

    129.002128.850128.291128.122

    126.383126.267122.104121.908

    120.216120.01177.31877.20377.00076.682

    58.99356.903

    48.15647.87638.34733.87331.78231.71531.68428.77928.10927.89324.30423.895

    22.34122.29422.27222.21913.96313.88913.864

    CC N

    O

    O

    CC N

    O

    O

    S SN N

    ppm (f2)1.02.03.04.05.06.07.08.0

    1.0

    2.0

    3.0

    4.0

    5.0

    6.0

    7.0

    8.0

    ppm (f1)

    COSY

  • S23

    2.903.003.103.203.303.403.503.603.70

    8.150

    8.200

    8.250

    8.300

    8.350

    ppm (t1)

    ppm (f2)1.02.03.04.05.06.07.08.0

    10

    20

    30

    40

    50

    60

    70

    80

    90

    100

    110

    120

    130

    140

    150ppm (f1)

    NOESY

    HSQC

  • S24

    ppm (t2)1.02.03.04.05.06.07.08.0

    10

    20

    30

    40

    50

    60

    70

    80

    90

    100

    110

    120

    130

    140

    150

    160

    170

    180

    190ppm (t1)

    HMBC

  • S25

    ppm (t1)1.02.03.04.05.06.07.08.09.0

    7.33

    67.

    332

    7.31

    67.

    303

    7.29

    87.

    264

    7.26

    07.

    254

    7.24

    27.

    214

    7.21

    17.

    207

    7.19

    27.

    178

    7.17

    47.

    138

    2.35

    92.

    340

    2.32

    01.

    495

    1.49

    01.

    476

    1.46

    21.

    456

    1.26

    91.

    259

    1.25

    01.

    241

    1.23

    21.

    223

    0.81

    50.

    811

    0.80

    60.

    797

    0.79

    10.

    779

    6.00

    8.084.04

    3.99

    4.95

    N

    O

    O

    ppm (t1)102030405060708090100110120130140150160170180190

    170.

    683

    141.

    073

    131.

    933

    128.

    815

    127.

    157

    125.

    595

    77.3

    1877

    .000

    76.6

    82

    31.7

    36

    28.2

    5123

    .780

    22.2

    8313

    .842

    N

    O

    O

    3,4-dipentyl-1-phenyl-1H-pyrrole-2,5-dione (13)