6
Tetrahedron
ACCEPTED MANUSCRIPT
4-Lithio-N3-(o-methoxyphenyl)-N6-benzoylsydnonimine (8b). In an
(N3-(o-Methoxyphenyl)-N6-benzoylsydnonimine-4-yl)-
NMR tube a dry sample of N3-(o-methoxyphenyl)-N6-benzoylsydnonimine
(0.022 g, 0.075 mmol) was dissolved in 0.4 mL of anhydrous THF-d8 under
an inert atmosphere. Then a 1M solution of LHMDS in THF (0.089 mL,
(triphenylphosphine)-gold(I) (12b). Under an inert atmosphere N3-(o-
methoxyphenyl)-N6-benzoylsydnonimine (0.054 g, 0.184 mmol) was
dissolved in 10 mL of THF (abs.). Then a 1M solution of LHMDS in THF
(0.22 mL, 0.221 mmol) was added and the mixture was cooled to -50 °C.
After adding chloro(triphenylphosphine)gold(I) (0.100 g, 0.202 mmol) the
mixture was stirred for 1 h, then slowly warmed to rt and stirred for another 2
h. Afterwards the solvent was evaporated in vacuo. The crude product is
purified by column chromatography (EE:PE = 3:1). Yield: 0.119 g (86 %) of
1
0.089 mmol) was added to give the lithium adduct in quantitative yields. H
NMR (600 MHz, THF-d8): δ = 8.25-8.24 (m, 2H, 9/9’-H), 7.48-7.51 (m, 1H,
15-H), 7.46-7.47 (m, 1H, 17-H), 7.22-7.25 (m, 1H, 11-H), 7.19-7.20 (m, 1H,
14-H), 7.13-7.16 (m, 2H, 10/10’-H), 7.05-7.07 (m, 1H, 16-H), 3.73 (s, 3H,
19-H) ppm. 13C NMR (150 MHz, THF-d8): δ = 185.4 (o, C5), 170.4 (o, C7),
159.8 (o, C4), 154.9 (o, C13), 140.8 (o, C8), 131.8 (+, C15), 130.8 (o, C12),
130.1 (+, C11), 129.8 (+, C9/C9‘), 128.2 (+, C17), 127.9 (+, C10/C10‘),
121.0 (+, C16), 113.4 (+, C14), 56.1 (+, C19) ppm.
1
a yellow solid, mp: 248 °C (decomposition); H NMR (600 MHz, CDCl3): δ
= 8.35-8.37 (m, 2H, 9/9‘-H), 7.57-7.58 (m, 1H, 17-H), 7.45-7.53 (m,
3x2H+3x1H+1H, 21/21‘/23/15-H), 7.34-7.37 (m, 2H, 10/10‘-H), 7.38-7.43
(m, 3x2H+2H+1H, 22/22‘/10/10‘/11-H), 7.04-7.07 (m, 1H, 16-H), 7.00-7.01
(m, 1H, 14-H), 3.70 (s, 3H, 19-H) ppm; 13C NMR (150 MHz, CDCl3): δ =
180.0 (o, d, JC,P = 7.6 Hz, C5), 172.0 (o, C7), 156.0 (o, d, JC,P = 126.5 Hz,
C4), 153.8 (o, C13), 139.4 (o, C8), 134.3 (+, d, JC,P = 14.2 Hz, C21/C21‘),
4-(Methylseleno)-molsidomine (11a). Under an inert atmosphere
Molsidomine (0.24 g, 1.00 mmol) was dissolved in 15 mL of THF (abs.).
Then a 1M solution of LHMDS in THF (1.20 mL, 1.20 mmol) was added and
the mixture was cooled to 0 °C. Selenium (0.10 g, 1.20 mmol) was added and
the mixture was stirred for 0.5 h. Then iodomethane (0.08 mL, 1.20 mmol)
was added. The mixture was stirred for an additional 0.5 h at 0 °C, then
slowly warmed to rt and stirred for another 2 h. Afterwards the solvent was
evaporated in vacuo. The crude product was purified by column
chromatography (DCM:MeOH 25:1). Yield: 0.282 g (84 %) of a brownish
solid, mp: 212 °C (decomposition); 1H NMR (400 MHz, CDCl3): δ = 4.17 (q,
3
2
2
1
132.1 (+, C15), 131.3 (+, C23), 130.2 (+, C11), 130.1 (o, d, JC,P = 55.6 Hz,
C20), 129.2 (+, C9/C9‘), 128.9 (+, d, JC,P = 11.3 Hz, C22/C22‘), 127.9 (o,
3
C12), 127.8 (+, C17), 127.6 (+, C10/C10‘), 120.2 (+, C16), 112.3 (+, C14),
55.9 (+, C19) ppm; 31P NMR (243 MHz, CDCl3): δ = 40.1 (s) ppm; IR
(ATR): 3051, 3018, 2963, 2839, 1596, 1563, 1498, 1435, 1335, 1282, 1254,
1099, 1022, 847, 746, 709, 690, 675, 536, 500 cm-1; MS (ESI 10 V) m/z (%)
= 754.2 (100) [M+H+]; HR-ESI-MS: calcd for C34H28N3O3PAu+ 754.1534.
Found 754.1533.
JH,H = 7.1 Hz, 2H, 9-H), 3.94 (t, JH,H = 4.5 Hz, 4H, 13/13‘-H), 3.49 (t, JH,H
=
4.5 Hz, 4H, 12/12‘-H), 2.39 (s, 16-H), 1.29 (t, JH,H = 7.1 Hz, 3H, 10-H) ppm;
13C NMR (100 MHz, CDCl3): δ = 186.6 (o, C5), 159.5 (o, C7), 98.4 (o, C4),
66.0 (- , C13/C13‘), 61.3 (-, C9), 55.3 (-, C12/C12‘), 14.5 (+, C10), 7.9 (+,
C16) ppm; 77Se NMR (114 MHz, CDCl3): δ = 97.2 (s) ppm; IR (ATR): 2972,
2932, 2900, 2858, 1662, 1592, 1405, 1371, 1198, 1146, 1100, 1056, 1042,
1024, 934, 882, 791 cm-1; MS (ESI 10 V) m/z (%) = 337.0 (100) [M+H+],
359.0 (40) [M+Na+], 695.0 (100) [2M+Na+]. HR-ESI-MS: calcd for
C10H17N4O4Se+ 337.0415. Found 337.0414.
trans-Chloro-(N3-morpholinyl-N6-ethylester-sydnonimine-4-yl)-bis-
(triphenylphosphine)-palladium(II) (13a). Under an inert atmosphere
Molsidomine (0.08 g, 0.33 mmol) was dissolved in 10 mL of THF (abs.).
Then a 1M solution of LHMDS in THF (0.40 mL, 0.40 mmol) was added and
the
mixture
was
cooled
to
-50
°C.
After
adding
bis(triphenylphosphine)palladium(II) dichloride (0.26 g, 0.36 mmol) the
mixture was stirred for 1 h, then slowly warmed to rt and stirred for another 2
h. Afterwards the solvent was evaporated in vacuo. The crude product was
purified by column chromatography (1. EE:PE = 3:1, 2. DCM:MeOH =
15:1). Yield: 0.211 g (70 %) of a yellow solid, mp: 197 °C (decomposition);
1H NMR (600 MHz, CDCl3): δ = 7.62-7.65 (m, 6x2H, 15/15‘-H), 7.40-7.43
(m, 6x1H, 17-H), 7.33-7.36 (m, 6x2H, 16/16‘-H), 3.95 (q, JH,H = 7.1 Hz, 2H,
9-H), 3.69 (t, JH,H = 4.5 Hz, 4H, 13/13‘-H), 2.76 (t, JH,H = 4.5 Hz, 4H, 12/12‘-
H), 1.18 (t, JH,H = 7.1 Hz, 3H, 10-H) ppm. 13C NMR (150 MHz, CDCl3): δ =
4-(Methylseleno)-N3-(o-methoxyphenyl)-N6-benzoylsydnonimine (11b).
Under an inert atmosphere N3-(o-methoxyphenyl)-N6-benzoylsydnonimine
(0.30 g, 1.00 mmol) was dissolved in 15 mL of THF (abs.). Then a 1M
solution of LHMDS in THF (1.20 mL, 1.20 mmol) was added and the
mixture was cooled to 0 °C. Selenium (0.10 g, 1.20 mmol) was added and the
mixture was stirred for 0.5 h. Then iodomethane (0.08 mL, 1.20 mmol) was
added. The mixture was stirred for an additional 0.5 h at 0 °C, then slowly
warmed to rt and stirred for another 2 h. Afterwards the solvent was
evaporated in vacuo. The crude product was purified by column
chromatography (DCM:MeOH 40:1). Yield: 0.255 g (66 %) of a brownish
2
174.8 (o, C5), 159.5 (o, C7), 134.7 (+, t, JC,P = 6.0 Hz, C15/C15‘), 130.6 (+,
C17), 130.2 (o, t, 1JC,P = 24.0 Hz, C14), 128.0 (+, t, 3JC,P = 5.3 Hz, C16/C16‘),
2
118.0 (o, t, JC,P = 8.2 Hz, C4), 65.9 (-, C13/C13‘), 60.2 (-, C9), 55.1 (-,
C12/C12‘), 14.8 (+, C10) ppm. 31P NMR (243 MHz, CDCl3): δ = 21.0 (s,
trans) ppm; traces of solvent are visible in the spectra. IR (ATR): 3053, 2969,
2859, 1631, 1541, 1481, 1434, 1280, 1237, 1176, 1094, 1061, 1040, 887, 743,
690, 509 cm-1; MS (ESI 0 V) m/z (%) = 907.3 (100) [M+H+]. HR-ESI-MS:
calcd for C45H44N4O4P2PdCl+ 907.1561. Found 907.1559.
1
solid, mp: 240 °C (decomposition); H NMR (400 MHz, CDCl3): δ = 8.32-
8.35 (m, 2H, 9/9’-H), 7.64-7.69 (m, 1H, 15-H), 7.47-7.51 (m, 1H, 11-H),
7.41-7.45 (m, 3H, 10/10’/17-H), 7.17-7.21 (m, 1H, 16-H), 7.15-7.17 (m, 1H,
14-H), 3.90 (s, 3H, 19-H), 2.38 (s, 3H, 21-H) ppm; 13C NMR (100 MHz,
CDCl3): δ = 172.8 (o, C7), 168.8 (o, C5), 153.3 (o, C13), 137.5 (o, C8), 134.0
(+, C15), 131.3 (+, C11), 129.6 (+, C9/C9’), 127.9 (+, C10/C10’), 127.0 (+,
C17), 122.5 (o, C12), 121.1 (+, C16), 112.5 (+, C14), 107.1 (+, C4), 56.1 (+,
C19), 7.4 (+, C21) ppm; 77Se NMR (114 MHz, CDCl3): δ = 106.9 (s) ppm; IR
(ATR): 3056, 2930, 2841, 1553, 1498, 1339, 1311, 1284, 1254, 1207, 1160,
1014, 978, 753, 704, 684 cm-1; MS (ESI 30 V) m/z (%) = 390.0 (100)
[M+H+], 799.2 (40) [2M+Na+]; HR-ESI-MS: calcd for C17H16N3O3Se+
390.0356. Found 390.0357.
trans-Chloro-(N3-(o-methoxyphenyl)-N6-benzoylsydnonimine-4-yl)-bis-
(triphenylphosphine)-palladium(II) (14b). Under an inert atmosphere N3-
(o-methoxyphenyl)-N6-benzoylsydnonimine (0.08 g, 0.28 mmol) was
dissolved in 10 mL of THF (abs.). Then a 1M solution of LHMDS in THF
(0.33 mL, 0.33 mmol) was added and the mixture was cooled to -50 °C. After
adding bis(triphenylphosphine)palladium(II) dichloride (0.21 g, 0.31 mmol)
the mixture was stirred for 1 h, then slowly warmed to rt and stirred for
another 2 h. Afterwards the solvent was evaporated in vacuo. The crude
product was purified by column chromatography (EE:PE = 3:1). Yield: 0.143
g (54%) of a yellow solid, mp: 212 °C (decomposition); 1H NMR (600 MHz,
CDCl3): δ = 8.07-8.09 (m, 2H, 9/9‘-H), 7.55-7.52 (m, 1H, 15-H), 7.46-7.49
(m, 6x2H, 21/21‘-H), 7.40-7.42 (m, 6x1H+1x2H, 23/11-H), 7.34-7.37 (m,
2H, 10/10‘-H), 7.26-7.29 (m, 6x2H, 22/22‘-H), 6.98-7.00 (m, 1H, 14-H),
6.75-6.78 (m, 1H, 16-H), 6.24-6.26 (m, 1H, 17-H), 3.13 (s, 3H, 19-H) ppm.
(N3-Morpholinyl-N6-ethoxycarbonyl-sydnonimine-4-yl)-
(triphenylphosphine)-gold(I) (12a). Under an inert atmosphere
Molsidomine (0.028 g, 0.118 mmol) was dissolved in 10 mL of THF (abs.).
Then a 1M solution of LHMDS in THF (0.141 mL, 0.141 mmol) was added
and the mixture was cooled to -50 °C. After adding
chloro(triphenylphosphine)gold(I) (0.064 g, 0.129 mmol) the mixture was
stirred for 1 h, then slowly warmed to rt and stirred for another 2 h.
Afterwards the solvent was evaporated in vacuo. The crude product was
purified by column chromatography (EE:PE 3:1). Yield: 0.041 g (50 %) of a
3
13C NMR (150 MHz, CDCl3): δ = 173.2 (o, t, JC,P = 3.3 Hz, C5), 170.7 (o,
2
C7), 153.8 (o, C13), 139.5 (o, C8), 134.4 (+, t, JC,P = 6.3 Hz, C21/C21‘),
132.2 (+, C15), 130.5 (+, C23), 130.0 (o, t, 1JC,P = 24.5 Hz, C20), 129.8 (+,
1
2
colorless solid, mp: 244 °C (decomposition); H NMR (600 MHz, CDCl3): δ
C11), 128.6 (+, C9/C9‘), 128.6 (o, t, JC,P = 7.8 Hz, C4), 128.4 (+, C17),
3
= 7.62-7.66 (m, 3x2H, 16/16‘-H), 7.52-7.55 (m, 3x1H, 18-H), 7.47-7.50 (m,
3x2H, 17/17‘-H), 4.14 (q, JH,H = 7.1 Hz, 2H, 9-H), 3.83 (t, JH,H = 4.5 Hz, 4H,
13/13‘-H), 4.64 (t, JH,H = 4.5 Hz, 4H, 12/12‘-H), 1.27 (t, JH,H = 7.1 Hz, 3H,
10-H) ppm; 13C NMR (150 MHz, CDCl3): δ = 180.8 (o, d, 3JC,P = 4.0 Hz, C5),
128.2 (+, t, JC,P = 5.0 Hz, C22/C22‘), 127.3 (+, C10/C10‘) 125.8 (o, C12),
120.2 (+, C16), 112.4 (+, C14), 55.5 (+, C19) ppm; 31P NMR (243 MHz,
CDCl3): δ = 20.8 (s, trans) ppm; traces of solvents are visible in the spectra.
IR (ATR): 3052, 2962, 1597, 1537, 1501, 1433, 1334, 1259, 1093, 1013, 798,
744, 690, 518 cm-1; MS (ESI 0 V) m/z (%) = 662.0 (100) [M-PPh3-Cl-], 960.2
(30) [M+H+]. HR-ESI-MS: calcd for C52H43N3O3P2PdCl+ 960.1503. Found
960.1503.
2
160.9 (o, C7), 145.2 (o, d, 2JC,P = 125.5 Hz, C4), 134.3 (+, d, JC,P = 14.0 Hz,
1
C16/C16‘), 130.6 (+, C18), 129.8 (o, d, JC,P = 56.0 Hz, C15), 129.1 (+, d,
3JC,P = 11.5 Hz, C17/C17‘), 66.3 (-, C13/C13‘), 60.4 (-, C9), 55.8 (-,
C12/C12‘), 14.7 (+, C10) ppm; 31P NMR (243 MHz, CDCl3): δ = 40.4 (s)
ppm; IR (ATR): 2972, 2922, 2894, 2855, 1631, 1553, 1435, 1283, 1247,
1193, 1100, 1062, 1039, 893, 751, 692, 536, 504 cm-1; MS (ESI 10 V) m/z
(%) = 701.2 (100) [M+H+]; HR-ESI-MS: calcd for C27H29N4O4PAu+
701.1592. Found 701.1592.
General procedure for the preparation of the compounds 14a-c.
Under a nitrogen atmosphere a sample of 2,5-dibromo-3,4-dinitrothiophene
(0.075 g, 0.2 mmol) was dissolved in 8 mL of anhydrous toluene and treated
with 10 mol% of the catalyst (complexes 13a,b). The mixture was then