Zwitterionic N,N-Dimethylisotryptammonium Carboxylate
FULL PAPER
were placed in a 20 mL flask under an argon atmosphere. A solution of
methyllithium in diethyl ether (2.71 mL, 1.6m, 4.34 mmol) was slowly
added. After stirring for 16 h, the yellow precipitate was collected by fil-
tration, washed three times with diethyl ether, and dried in vacuo. The
5.85. For X-ray structure determination, a single crystal was obtained by
recrystallization from methanol.
Spiro[10,11-dihydro-5H-dibenzo
oxa-4’-silacyclohexan-2’-one[4’a,9’b-b’]-5’-[2“-(N,N-dimethylamino)eth-
yl]indole})] (5): A 100 mL Schlenk flask was charged with a suspension
ACHTUNGTREN[NUNG a,d]cycloheptene-5,1’-(4’,4’-diphenyl{3’-
title compound was obtained as
a yellow, highly moisture-sensitive
AHCTUNGTRENNUNG
powder (574 mg, 1.32 mmol). Yield: 95%.
of
dibenzo
5-{1-[2-(N,N-dimethylamino)ethyl]indol-3-yl}-10,11-dihydro-5H-
[a,d]cycloheptene-5-carboxylic acid (2.0 g, 4.7 mmol) in diethyl
5-(2-Deutero{1-[2-(N,N-dimethylamino)ethyl]indol-3-yl})-10,11-dihydro-
U
5H-dibenzo
lithio{1-[2-(N,N-dimethylamino)ethyl]indol-3-yl})-10,11-dihydro-5H-
dibenzo[a,d]cycloheptene-5-carboxylate (100 mg, 229 mmol) and diethyl
ether (2 mL) were placed in a 10 mL flask under an argon atmosphere.
Addition of D2O (1 mL) to the yellow suspension led to the precipitation
of a colorless solid, which was collected by filtration, washed with water
and diethyl ether, and dried in vacuo. The product was obtained as a col-
orless powder (92.7 mg, 217 mmol). Yield: 95%; 1H NMR (250 MHz,
[D6]DMSO/1% F3CCOOD, 258C): d=7.53–7.51 (m, 1H; Hindole), 7.20–
[a,d]cycloheptene-5-carboxylic acid ([D1]1): Lithium 5-(2-
ether (20 mL) under an argon atmosphere. A solution of methyllithium
in diethyl ether (6.50 mL, 1.6m, 10.4 mmol, 2.2 equiv) was slowly added
by means of a syringe. The reaction mixture was stirred for 16 h at room
temperature. The resulting yellow suspension was cooled to À788C,
ACHTUNGTRENNUNG
whereupon
a pre-cooled solution of dichlorodiphenylsilane (2.98 g,
2.48 mL, 11.8 mmol) in THF (30 mL) was injected into the flask. The re-
action mixture was stirred and allowed to warm to room temperature
overnight, yielding a violet suspension. The colorless precipitate was re-
moved by filtration. The remaining violet solution was concentrated in
vacuo to give the crude product as a viscous oil. Purification by column
chromatography on silica gel (dichloromethane/methanol, 9:1) yielded a
yellow solid. It was recrystallized from dichloromethane/methanol and
the title compound was obtained as light-yellow crystals (1.29 g,
2.13 mmol). Yield: 45%; Rf =0.70 (CH2Cl2/MeOH, 9:1); m.p. 2398C;
1H NMR (500 MHz, [D6]DMSO, 258C): d=7.75–7.73 (m, 4H; Hphenyl),
7.70–7.67 (m, 2H; Hphenyl), 7.63–7.59 (m, 4H; Hphenyl), 7.48–7.45 (m, 1H;
7-Hindole), 7.25–7.23 (m, 2H; Haryl), 7.13–7.07 (m, 3H; 6-Hindole, Haryl),
6.98–6.96 (m, 2H; Haryl), 6.87–6.84 (m, 2H; Haryl), 6.74–6.70 (m, 1H; 5-
6.89 (m, 9H; 1 ꢁ Hindole, 8 ꢁ Haryl), 6.73–6.69 (m, 1H; Hindole), 6.49–6.45
3
(m, 1H; Hindole), 4.61 (t, J
N
ACHTUGNTREN(UNNG CH3)2), 3.51 (t,
3J
(s, 6H; N
Spiro[10,11-dihydro-5H-dibenzo
oxa-4’-silacyclohexan-2’-one[4’a,9’b-b’]-5’-[2“-(N,N-dimethylamino)eth-
yl]indole})] (4): A 100 mL Schlenk flask was charged with a suspension
A
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
AHCTUNGTREGUN[NN a,d]cycloheptene-5,1’-(4’,4’-dimethyl{3’-
ACHTUNGTRENNUNG
of
dibenzo
5-{1-[2-(N,N-dimethylamino)ethyl]indol-3-yl}-10,11-dihydro-5H-
[a,d]cycloheptene-5-carboxylic acid (2.0 g, 4.7 mmol) in diethyl
U
Hindole), 6.59–6.57 (m, 1H; 4-Hindole), 4.29 (t, 3J
CH2CH2N(CH3)2), 3.63–3.57 (m, 2H; CH2), 3.20–3.14 (m, 2H; CH2), 2.22
(t, 3J
(H,H)=7.0 Hz, 2H; CH2NACHTUNGTRENN(UG CH3)2), 1.92 ppm (s, 6H; NACHTUNGTRENNUNG(CH3)2);
ACHTUNGTREN(NGNU H,H)=7.0 Hz, 2H;
ether (20 mL) under an argon atmosphere. A solution of methyllithium
in diethyl ether (6.5 mL, 1.6m, 10 mmol, 2.2 equiv) was slowly added by
means of a syringe. The reaction mixture was stirred for 16 h at room
temperature. The resulting yellow suspension was cooled to À788C,
AHCTUNGTRENNUNG
G
1H NMR (250 MHz, CDCl3, 258C): d=7.80–7.75 (m, 4H; Hphenyl), 7.61–
7.44 (m, 6H; Hphenyl), 7.35 (d, 3JH,H =8.3 Hz, 1H; Hindole), 7.20–7.02 (m,
whereupon
a pre-cooled solution of dichlorodimethylsilane (1.8 g,
7H; Hindole/aryl), 6.86–6.67 (m, 4H; Hindole/aryl), 4.35 (t, 3J
ACHTUNGTRENNUNG
1.7 mL, 14 mmol) in THF (30 mL) was injected into the flask. The reac-
tion mixture was stirred at room temperature overnight. The solvent was
then removed in vacuo. Diethyl ether was added to the initially orange
crude product, stirred for a few hours, and filtered. This process was re-
peated twice more. The nearly colorless powder was recrystallized from
methanol to afford the title compound as colorless crystals (1.71 g,
3.55 mmol). Yield: 76%; m.p. 2048C; 1H NMR (300 MHz, [D6]DMSO,
258C): d=7.51–7.48 (m, 1H; 7-Hindole), 7.23–7.19 (m, 2H; Haryl), 7.08–7.04
(m, 3H; 5-Hindole, Haryl), 7.00–6.85 (m, 4H; Haryl), 6.70–6.64 (m, 1H; 6-
2H; CH2CH2N
ACHTUNGTRENNUNG
2.35 (t, 3J
G
1H NMR (250 MHz, [D8]THF, 258C): d=7.82–7.78 (m, 4H; Hphenyl),
7.62–7.45 (m, 6H; Hphenyl), 7.39–7.34 (m, 1H; Hindole), 7.17–7.13 (m, 2H;
Hindole/aryl), 7.08–6.97 (m, 5H; Hindole/aryl), 6.79–6.71 (m, 2H; Hindole/aryl),
6.66–6.63 (m, 2H; Hindole/aryl), 4.32 (t, 3J
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
A
R
NACHTUNGTRENNUNG
13C{1H} NMR (125 MHz, [D6]DMSO, 258C): d=170.4 (CO2), 143.2
(Caryl), 140.1 (7a-Cindole), 139.8 (Caryl), 135.1 (CHphenyl), 133.5 (3-Cindole),
132.2 (CHphenyl), 131.8 (CHaryl), 130.5 (CHaryl), 129.9 (Cphenyl), 128.9
(CHphenyl), 127.5 (2-Cindole), 127.1 (CHaryl), 125.9 (CHaryl), 125.6 (3a-Cindole),
123.7 (6-CHindole), 120.7 (4-CHindole), 119.5 (5-CHindole), 110.6 (7-CHindole),
Hindole), 6.55–6.51 (m, 1H; 4-Hindole), 4.44 (t, 3J
CH2CH2N(CH3)2), 3.62–3.54 (m, 2H; CH2), 3.19–3.11 (m, 2H; CH2), 2.81
(t, 3J
(H,H)=6.3 Hz, 2H; CH2N(CH3)2), 2.36 (s, 6H; N(CH3)2), 0.77 ppm
(s, 6H; Si
(CH3)2); 1H NMR (250 MHz, CDCl3, 258C): d=7.34–7.32 (m,
ACHTUNGTREN(NGNU H,H)=6.3 Hz, 2H;
ACHTUNGTRENNUNG
A
R
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
1H; Hindole), 7.18–7.03 (m, 5H; 1 ꢄ Hindole, 4 ꢄ Haryl), 6.91–6.83 (m, 4H;
Haryl), 6.73–6.71 (m, 1H; Hindole), 6.63–6.61 (m, 1H; Hindole), 4.47 (t, 3J-
63.9 (C
ACTHGNUTERN(UGNN CO2)), 57.8 (CH2NAHCTNUREGTN(GNUN CH3)2), 46.0 (CH2CH2NACHTNUGTREN(NUGN CH3)2), 45.1 (N-
AHCTNUGTREN(GUNN CH3)2), 36.0 ppm (CH2); IR (KBr): n˜ =3450 (br), 3050 (w), 3019 (w),
A
ACHTUNGTRENNUNG
2942 (w), 2822 (w), 2771 (w), 1733 (s), 1489 (m), 1447 (w), 1430 (m),
1359 (m), 1326 (w), 1174 (s), 1120 (s), 1110 (s), 977 (s), 885 (m), 825 (w),
740 (s), 719 (m), 700 (s), 611 (w), 513 (s), 493 cmÀ1 (m); MS (ESI+): m/z
(%): 722.5 (9), 605.3 (100) [M+H+]; MS (ESI-): m/z (%): 635.3 (44)
[MÀ+MeO], 623.3 (62), 591.3 (27), 283.3 (54), 255.2 (100); HRMS
(ESI+): calcd (m/z) for C40H37N2O2Si+: 605.26227; found: 605.26243; ele-
mental analysis calcd (%) for C40H36N2O2Si: C 79.43, H 6.00, N 4.63;
found: C 79.14, H 6.04, N 4.70. For X-ray structure determination, a
single crystal was obtained by recrystallization from dichloromethane/
methanol.
G
ACHTUNGTRENNUNG
N
A
ACHTUNGTRENNUNG
[D8]THF, 258C): d=7.40–7.36 (m, 1H; Hindole), 7.16–7.11 (m, 2H; Hindole/
aryl), 7.06–6.93 (m, 5H; Hindole/aryl), 6.84–6.78 (m, 2H; Hindole/aryl), 6.65–6.58
(m, 2H; Hindole/aryl), 4.39 (t, 3J
A
ACHTUGNRTNE(NUNG CH3)2),
AHCTUNGTRENNUNG
E
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
142.9 (Caryl), 140.2 (Caryl), 139.5 (7a-Cindole), 131.7 (CHaryl), 131.7 (3a-
Cindole), 130.4 (2-Cindole), 130.2 (CHaryl), 126.7 (CHaryl), 125.9 (CHaryl), 125.3
(3-Cindole), 123.0 (4-CHindole), 120.3 (5-CHindole), 119.2 (6-CHindole), 110.2 (7-
Spiro[10,11-dihydro-5H-dibenzoACHTNUTRGNEUNG[a,d]cycloheptene-5,1’-(4’,4’-di-nbutyl{3’-
CHindole), 63.4 (C
(CO2)), 57.8 (CH2N
E
E
oxa-4’-stannacyclohexan-2’-one[4’a,9’b-b’]-5’-[2“-(N,N-dimethylamino)-
ethyl]indole})] (6): A 150 mL Schlenk flask was charged with a suspen-
sion of 5-{1-[2-(N,N-dimethylamino)ethyl]indol-3-yl}-10,11-dihydro-5H-
45.2 (N(CH3)2), 36.0 (CH2), 0.9 ppm (SiACTHUNGTRENNUNG
A
3056 (w), 3016 (w), 2941 (br), 2895 (w), 2822 (w), 2772 (w), 1727 (s),
1636 (w), 1487 (m), 1449 (m), 1359 (m), 1326 (w), 1258 (s), 1207 (br), 981
(s), 889 (s), 851 (s), 799 (s), 776 (s), 753 (s), 742 (s), 690 cmÀ1 (w); MS
(ESI+): m/z (%): 967.5 (41) [2M+Li+], 961.5 (30) [2M+H+], 519.2 (11)
[M+K+], 487.2 (100) [M+Li+], 481.4 (63) [M+H+], 425.2 (2) [1+H]+;
MS (ESI-): m/z (%): 719.2 (13) [M+3·(Si(Me)2O)+OHÀ], 645.2 (37)
[M+2·(Si(Me)2O)+OHÀ], 571.2 (65) [M+(Si(Me)2O)+OHÀ], 497.3 (99)
[M+OHÀ], 423.3 (100) [MÀÀ(Si(Me)2)+H]; HRMS (ESI+): calcd (m/z)
for C30H33N2O2Si+: 481.23058; found: 481.23112; elemental analysis calcd
(%) for C30H32N2O2Si: C 74.96, H 6.71, N 5.83; found: C 75.05, H 6.80, N
dibenzoACTHUNRTGNEUNG[a,d]cycloheptene-5-carboxylic acid (4.0 g, 9.4 mmol) in diethyl
ether (40 mL) under an argon atmosphere. A solution of methyllithium
in diethyl ether (13.0 mL, 1.6m, 20.7 mmol, 2.2 equiv) was slowly added
by means of a syringe. The reaction mixture was stirred for 16 h at room
temperature. The resulting yellow suspension was cooled to À788C,
whereupon a pre-cooled solution of dibutyltin dichloride (3.7 g, 12 mmol)
in THF (60 mL) was injected into the flask. The reaction mixture was
stirred and allowed to warm to room temperature overnight, and then
the solvent was removed in vacuo. Diethyl ether was added to the orange
Chem. Eur. J. 2012, 00, 0 – 0
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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