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DOI: 10.1055/s-2003-40837
A New Way to 2-Methylbenzo- and Pyridoindoles
Publication History
Publication Date:
24 July 2003 (online)
Abstract
Allyltriphenylphosphonium chloride reacts with some 1-nitronaphthalene and 5-nitroquinoline derivatives in the presence of Ti(i-PrO)4 and DBU to give 1-hydroxyindoles, which can be reduced in situ to the corresponding indoles.
Key words
cyclizations - heterocycles - indoles - nucleophilic additions - ylides
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References
Standard procedure: To the slurry of 1 (2.5 mmol) and 2 (1 g,
3 mmol) in dry HMPA (2.5 mL), Ti(i-PrO)4 (1.85
mL, 6.25 mmol) was added followed by the addition of DBU (1.9 mL,
12.5 mol). The slurry was stirred at room temperature for the time
specified in the table until HPLC analysis showed complete conversion
of the substrate. At this point MeOH (5 mL) was added followed by
Et3N (1 mL) and then ethyl bromoacetate (330 µL,
3 mmol), and the mixture stirred further until HPLC analysis showed
complete conversion. Then, the mixture was diluted with ethyl acetate and
ca. 5 mL of sat aq NH4Cl solution was added. The mixture
was stirred for 20 min, filtered through a Celite pad, diluted with
water, extracted with ethyl acetate and chromatographed. Selected
spectral data (1H NMR: 400 MHz, CDCl3;
Ms: 70 eV): 3a: δH = 2.37
(s, 3 H), 6.01 (broad s, 1 H), 6.88-6.94 (m, 1 H), 7.17
(ddd, J = 8.0 Hz, 6.8 Hz, 1.1
Hz, 1 H), 7.26-7.30 (m, 1 H), 7.40 (d, J = 8.4
Hz, 1 H), 7.72 (d, J = 8.0 Hz,
1 H), 8.34 (d, J = 8.4 Hz, 1
H), 8.69 (broad s, 1 H); HRMS: 197.0847; calcd. for C13H11ON: 197.0841;
(1H NMR: 500 MHz, CDCl3; MS: 70 eV): 4a:
δH = 2.50
(d, J = 0.9, 3 H), 6.34-6.37
(m, 1 H), 7.36 (ddd,
J = 8.2
Hz, 6.9 Hz, 1.3 Hz, 1 H), 7.46 (d, J = 8.5
Hz, 1 H overlapped on ddd, J = 8.3
Hz, 7.0 Hz, 1.3 Hz, 1 H), 7.61 (dd, J = 8.5
Hz, 0.9 Hz, 1 H), 7.87-7.88 (m, 1 H), 7.89-7.90
(m, 1 H), 8.51 (broad s, 1 H); δC = 132.99,
130.11, 129.89, 128.87, 125.22, 124.85, 123.20, 121.34, 120.37,
120.22, 119.00, 102.18, 13.73; HRMS: 181.0895; calcd. for C13H11N:
181.0892; 4b: δH = 1.29
(s, 9 H), 2.53 (d, J = 0.8 Hz,
3 H), 6.35-6.36 (m, 1 H), 7.45 (ddd, J = 8.2
Hz, 6.8 Hz, 1.3 Hz, 1 H), 7.50 (ddd, J = 8.2
Hz, 6.8 Hz, 1.3 Hz, 1 H), 7.90-7.92 (m, 1 H), 8.00 (s,
1 H), 8.60 (br s, 1 H), 8.82-8.84 (m, 1 H); δC = 133.47,
132.58, 132.41, 131.31, 128.82, 125.37, 124.36, 123.56, 121.79,
121.44, 119.15, 47.03, 31.20, 13.71; HRMS: 269.1246; calcd. for
C17H19NS: 269.1238; 4c: δH = 2.48
(d, J = 0.8 Hz, 3 H), 3.99 (s,
3 H), 6.26-6.27 (m, 1 H), 6.96 (s, 1 H), 7.37 (ddd, J = 8.2 Hz, 6.9 Hz, 1.2 Hz,
1 H), 7.48 (ddd, J = 8.2 Hz,
6.9 Hz, 1.2 Hz, 1 H), 7.80-7.81 (m, 1 H), 8.28-8.29
(m, 1 H), 8.36 (br s, 1 H);
δC = 150.18,
132.92, 125.92, 125.16, 124.11, 123.34, 122.88, 122.71, 121.85,
118.82, 102.04, 97.99, 55.82, 13.73; HRMS: 211.0998; calcd. for
C14H13NO: 211.0997; 4d: δH = 2.55
(d, J = 0.8 Hz, 3 H), 6.37-6.39
(m, 1 H), 6.94 (part AA′, 2 H), 7.07 (part BB′,
2 H), 7.40 (ddd, J = 8.3 Hz,
6.9 Hz, 1.2 Hz, 1 H), 7.52 (ddd, J = 8.2
Hz, 6.9 Hz, 1.2 Hz, 1 H), 7.96-7.98 (m, 1 H), 8.39-8.41
(m, 1 H), 8.70 (broad s, 1 H); δC = 138.35,
133.86, 131.67, 130.84, 130.51, 130.14, 128.78, 127.55, 127.30,
125.95, 124.74, 124.52, 122.25, 119.57, 119.27, 102.45, 13.73; HRMS:
323.0535; calcd. for C19H14NS35Cl:
323.0536; 4e: δH = 2.56
(d, J = 0.8 Hz, 3 H), 6.40-6.41
(m, 1 H), 7.39 (dd, J = 8.3
Hz, 4.3 Hz, 1 H), 7.76 (dd, J = 8.8
Hz, 0.8 Hz, 1 H), 7.85 (d, J = 8.8
Hz, 1 H), 8.30 (ddd, J = 8.3
Hz, 1.7 Hz, 0.8 Hz, 1 H), 8.81 (dd, J = 4.3
Hz, 1.7 Hz, 1 H), 8.89 (br s, 1 H); δC = 146.99,
145.71, 134.40, 127.38, 125.12, 123.84, 121.66, 120.95, 119.96,
116.52, 102.43, 13.80; HRMS: 182.0841; calcd. for C12H10N2: 182.0844; 4f: δH = 2.46
(d, J = 0.8 Hz, 3 H), 4.00 (s,
3 H), 6.31-6.33 (m, 3 H), 7.32 (dd, J = 8.3
Hz, 4.3 Hz, 1 H), 8.77 (dd, J = 4.3
Hz, 1.7 Hz, 1 H), 9.75 (br s, 1 H); δC = 149.72, 145.62,
137.83, 134.75, 127.98, 124.17, 123.87, 120.65, 117.50, 55.88, 13.63;
HRMS: 21.0946; calcd. for C13H12N2O:
212.0949.