New Entry to Bridged Pentacyclic
Indolyltetrahydroisoquinoline Skeleton via Tandem S-Alkylation and
Intramolecular C-Alkylation

Firouz Matloubi Moghaddam; Salman Taheri; Zohreh Mirjafary; Hamdollah Saeidian

doi:10.1055/s-0029-1218534

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Synlett 2010(1): 123-127
DOI: 10.1055/s-0029-1218534

LETTER

New Entry to Bridged Pentacyclic Indolyltetrahydroisoquinoline Skeleton via Tandem S-Alkylation and Intramolecular C-Alkylation

Firouz Matloubi Moghaddam*, Salman Taheri, Zohreh Mirjafary, Hamdollah Saeidian
Laboratory of Organic Synthesis & Natural Products, Department of Chemistry, Sharif University of Technology, P. O. Box 11155-9516, Tehran, Iran
e-Mail: matloubi@sharif.edu;

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Publication History

Received 18 August 2009
Publication Date:
02 December 2009 (online)

Abstract
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Abstract

An efficient, single-step synthesis of hitherto unknown indole-annulated pentacyclic indolylhydroisoquinolines via tandem S-alkylation and intramolecular C-alkylation of indolin-2-thiones with N-alkylisoquinolinium salts is reported. This new approach provides a powerful entry into polycyclic structures containing nitrogen and sulfur related to alkaloids.

Key words

thiooxindoles - pentacyclic heterocycles - tandem reaction - indolyltetrahydroisoquinoline - isoquinolinium salts

References and Notes

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16

Spectroscopic Data5-Ethyl-14-methyl-5,7,12,13-tetrahydro-7,13-epimino[2]benzothiocino[3,4- b ]indole (3a)
Pale yellow solid; mp 163-165 ˚C. ^¹H NMR (500 MHz, CDCl₃): δ = 7.54 (d, J = 7.5 Hz, 1 H), 7.37 (d, J = 8.0 Hz, 1 H), 7.13-7.32 (m, 5 H), 7.05 (d, J = 7.5 Hz, 1 H), 5.78 (s, 1 H), 4.53 (d, J = 5.5 Hz, 1 H), 4.06 (m, 2 H), 3.61 (dd, J = 15.5, 5.5 Hz, 1 H), 3.15 (d, J = 15.5 Hz, 1 H), 2.65 (s, 3 H), 1.31 (t, J = 7.1 Hz, 3 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 137.4 (C), 136.1 (C), 132.9 (C), 129.6 (CH), 128.0 (C), 127.9 (C), 127.8 (CH), 127.6 (CH) 126.1 (CH), 120.4 (CH), 119.3 (CH), 116.6 (CH), 108.7 (CH), 101.8 (C), 71.7 (CH), 52.6 (CH), 42.0 (CH₃), 38.4 (CH₂), 36.6 (CH₂), 15.4 (CH₃). Anal. Calcd for C₂₀H₂₀N₂S: C, 74.96; H, 6.29; N, 8.74. Found: C, 75.01; H, 6.31; N, 8.77.
14-Ethyl-5,7,12,13-tetrahydro-7,13-epimino[2]-benzothiocino[3,4- b ]indole (3b)
White solid; mp 107-109 ˚C. ^¹H NMR (500 MHz, CDCl₃): δ = 7.60 (br s, NH, 1 H), 7.47 (d, J = 7.5 Hz, 1 H), 7.36 (d, J = 8.0 Hz, 1 H), 7.25 (d, J = 7.5 Hz, 1 H), 7.19 (t, J = 8.0 Hz, 1 H), 7.10-7.16 (m, 3 H), 7.03 (d, J = 8.0 Hz, 1 H), 5.86 (s, 1 H), 4.60 (d, J = 5.0 Hz, 1 H), 3.55 (dd, J = 16.0, 5.0 Hz, 1 H), 3.12 (d, J = 16.0 Hz, 1 H), 2.88 (m, 1 H), 2.73 (m, 1 H), 1.30 (t, J = 7.0 Hz, 3 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 137.4 (C), 5.3 (C), 135.2 (C), 129.6 (CH), 127.9 (CH), 127.6 (CH), 127.4 (C), 126.7 (C), 126.2 (CH), 121.1 (CH), 119.9 (CH), 116.6 (CH), 116.5 (C), 110.5 (CH), 103.1 (C), 70.2 (CH), 50.6 (CH), 47.8 (CH₂), 36.5 (CH₂), 13.1 (CH₃). Anal. Calcd for C₁₉H₁₈N₂S: C, 74.47; H, 5.92; N, 9.14. Found: C, 74.92; H, 6.11; N, 9.25.
14-Benzyl-5,7,12,13-tetrahydro-7,13-epimino[2]-benzothiocino[3,4- b ]indole (3c)
Yellow solid; mp 88-90 ˚C. ^¹H NMR (500 MHz, CDCl₃): δ = 7.68 (br s, NH, 1 H), 7.48 (d, J = 7.0 Hz, 2 H), 7.44 (d, J = 7.5 Hz, 1 H), 7.38 (t, J = 8.0 Hz, 2 H), 7.12-7.36 (m, 7 H), 7.04 (d, J = 7.5 Hz, 1 H), 5.72 (s, 1 H), 4.58 (d, J = 5.5 Hz, 1 H), 4.02 (d, J = 13.5 Hz, 1 H), 3.85 (d, J = 13.5 Hz, 1 H), 3.59 (dd, J = 16.0, 5.5 Hz, 1 H), 3.10 (d, J = 16.0 Hz, 1 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 138.0 (C), 137.4 (C), 135.4 (C), 133.3 (C), 129.6 (CH), 129.5 (CH), 128.9 (CH), 127.9 (CH), 127.8 (CH), 127.6 (CH), 127.3 (C), 126.6 (C), 126.1 (CH), 121.2 (CH), 119.9 (CH), 116.7 (CH), 110.5 (CH), 103.1 (C), 70.2 (CH), 58.1 (CH₂), 50.8 (CH), 36.5 (CH₂). Anal. Calcd for C₂₄H₂₀N₂S: C, 78.23; H, 5.47. N, 7.60. Found: C, 78.66; H, 5.83; N, 7.63.
14-Prop-2-yn-1-yl-5,7,12,13-tetrahydro-7,13-epimino[2]-benzothiocino[3,4- b ]indole (3d)
White solid; mp 131-133 ˚C. ^¹H NMR (500 MHz, CDCl₃): δ = 7.65 (s, 1 H, NH), 7.49 (d, J = 7.5 Hz, 1 H), 7.38 (d, J = 7.5 Hz, 1 H), 7.12-7.26 (m, 5 H), 7.03 (d, J = 7.5 Hz, 1 H), 6.01 (s, 1 H), 4.68 (d, J = 5.5 Hz, 1 H), 3.62 (dd, J = 16.0, 2.5 Hz, 1 H), 3.61 (dd, J = 15.5, 5.5 Hz, 1 H), 3.51 (dd, J = 16.0, 2.5 Hz, 1 H), 3.13 (d, J = 15.5 Hz, 1 H), 3.39 (t, J = 2.5 Hz, 1 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 136.8 (C), 135.5 (C), 132.9 (C), 129.5 (CH), 128.0 (CH), 127.7 (CH), 127.1 (C), 126.3 (CH), 125.8 (C), 121.4 (CH), 120.1 (CH), 116.7 (CH), 110.6 (CH), 102.7 (C), 79.8 (C), 73.7 (C), 68.3 (CH), 51.0 (CH), 43.2 (CH₂), 36.5 (CH₂). Anal. Calcd for C₂₀H₁₆N₂S: C, 75.92; H, 5.10; N, 8.85. Found: C, 75.62; H, 5.23; N, 8.83.
14-Methyl-5,7,12,13-tetrahydro-7,13-epimino[2]-benzothiocino[3,4- b ]indole (3e)
Yellow solid; mp 125-127 ˚C. ^¹H NMR (500 MHz, CDCl₃): δ = 7.67 (br s, NH, 1 H), 7.49 (d, J = 7.5 Hz, 1 H), 7.36 (d, J = 8.0 Hz, 1 H), 7.11-7.22 (m, 5 H), 7.04 (d, J = 7.5 Hz, 1 H), 5.73 (s, 1 H), 4.49 (d, J = 5.0 Hz, 1 H), 3.59 (dd, J = 16.0, 5.0 Hz, 1 H), 3.13 (d, J = 16.0 Hz, 1 H), 2.67 (s, 3 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 137.36 (C), 135.42 (C), 132.8 (C), 129.6 (CH), 127.9 (CH), 127.5 (CH), 127.4 (C), 126.2 (CH), 126.1 (C), 121.2 (CH), 119.9 (CH), 116.6 (CH), 110.6 (CH), 102.7 (C), 72.0 (CH), 52.3 (CH), 42.0 (CH₃), 36.5 (CH₂). Anal. Calcd for C₁₈H₁₆N₂S: C, 73.94; H, 5.52 N, 9.58. Found: C, 74.12; H, 5.71; N, 9.55.
5,14-Dimethyl-5,7,12,13-tetrahydro-7,13-epimino[2]-benzothiocino[3,4- b ]indole (3f)
Yellow solid; mp 164-166 ˚C. ^¹H NMR (500 MHz, CDCl₃): δ = 7.51 (m, 1 H), 7.37 (d, J = 7.5 Hz, 1 H), 7.13-7.28 (m, 5 H), 7.04 (d, J = 7.5 Hz, 1 H), 5.78 (s, 1 H), 4.52 (d, J = 5.0 Hz, 1 H), 3.60 (dd, J = 15.5, 5.5 Hz, 1 H), 3.56 (s, 3 H), 3.15 (d, J = 15.5 Hz, 1 H), 2.63 (s, 3 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 137.4 (C), 137.1 (C), 132.9 (C), 129.5 (CH), 128.9 (C), 127.9 (CH), 127.6 (CH), 126.1 (CH), 119.3 (CH), 116.5 (CH), 108.5 (CH), 101.7 (C), 71.9 (CH), 52.6 (CH), 41.9 (CH₃), 36.6 (CH₂), 29.7 (CH₃). Anal. Calcd for C₁₉H₁₈N₂S: C, 74.47; H, 5.92; N, 9.14. Found: C, 74.32; H, 6.11; N, 9.18.
14-Methyl-5-phenyl-5,7,12,13-tetrahydro-7,13-epimino[2]benzothiocino[3,4- b ]indole (3g)
Yellow solid; mp 170-172 ˚C. ^¹H NMR (500 MHz, CDCl₃): δ = 7.59 (d, J = 8.0 Hz, 1 H), 7.53 (t, J = 7.5 Hz, 1 H), 7.52 (d, J = 7.5 Hz, 1 H), 7.43 (m, 3 H), 7.30 (t, J = 8.5 Hz, 2 H), 7.23 (t, J = 7.5 Hz, 1 H), 7.08-7.18 (m, 4 H), 5.69 (s, 1 H), 4.58 (d, J = 5.0 Hz, 1 H), 3.66 (dd, J = 16.0, 5.0 Hz, 1 H), 3.24 (d, J = 16.0 Hz, 1 H), 2.69 (s, 3 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 137.45 (C), 137.4 (C), 137.2 (C), 132.7 (C), 129.7 (CH), 129.6 (CH), 129.0 (CH), 128.2 (CH), 128.0 (CH), 127.8 (CH), 127.7 (CH), 127.4 (CH), 126.2 (CH), 121.3 (CH), 120.4 (CH), 116.6 (CH), 109.9 (CH), 103.5 (C), 71.4 (CH), 52.6 (CH), 42.1 (CH₃), 36.5 (CH₂). Anal. Calcd for C₂₂H₂₀N₂S: C, 78.23; H, 5.47; N, 7.60. Found: C, 78.37; H, 5.80; N, 7.64.
14-Prop-2-yn-1-yl-5,7,12,13-tetrahydro-7,13-epimino[2]benzothiocino[3,4- b ]indole (3h)
Yellow solid; mp 183-185 ˚C; ^¹H NMR (500 MHz, CDCl₃): δ = 7.79 (d, J = 8.0 Hz, 1 H), 7.49-7.56 (m, 4 H), 7.04-7.46 (m, 4 H), 7.10-7.26 (m, 5 H), 5.63 (s, 1 H), 5.41 (d, J = 6.0 Hz, 1 H), 3.86 (dd, J = 16.0, 6.0 Hz, 1 H), 3.31-3.40 (m, 3 H), 2.38 (t, J = 2.5 Hz, 1 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 138.4 (C), 137.3 (C), 137.1 (C), 133.4 (C), 129.8 (CH), 129.6 (CH), 129.4 (C), 128.1 (C), 127.9 (CH), 127.6 (CH), 127.3 (CH), 125.2 (CH), 121.2 (CH), 120.3 (CH), 116.6 (CH), 109.8 (CH), 103.9 (C), 80.3 (C) 74.6 (C) 69.3 (CH), 50.9 (CH), 47.8 (CH₂), 36.6 (CH₂).
14-Ethyl-5-phenyl-5,7,12,13-tetrahydro-7,13-epimino[2]benzothiocino[3,4- b ]indole (3i)
Pale yellow solid; mp 178-180 ˚C. ^¹H NMR (500 MHz, CDCl₃): δ = 7.57 (d, J = 7.5 Hz, 1 H), 7.51 (t, J = 7.5 Hz, 2 H), 7.30-7.43 (m, 5 H), 7.20 (t, J = 7.5 Hz, 1 H), 7.07-7.18 (m, 4 H), 5.82 (s, 1 H), 4.68 (d, J = 5.0 Hz, 1 H), 3.62 (dd, J = 15.5, 5.5 Hz, 1 H), 3.22 (d, J = 15.5 Hz, 1 H), 2.92 (m, 1 H), 2.78 (m, 1 H), 1.32 (t, J = 7.2 Hz, 3 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 137.4 (C), 137.2 (C), 137.1 (C), 133.1 (C), 129.7 (CH), 129.6 (CH), 129.5 (C), 128.1 (C), 127.9 (CH), 127.8 (CH), 127.3 (CH), 126.2 (CH), 121.2 (CH), 120.3 (CH), 116.6 (CH), 109.8 (CH), 103.9 (C), 69.3 (CH), 50.9 (CH), 47.8 (CH₂), 36.6 (CH₂), 13.2 (CH₃).
14-Ethyl-5-methyl-5,7,12,13-tetrahydro-7,13-epimino[2]benzothiocino[3,4- b ] indole (3j)
Pale yellow solid; mp 167-169 ˚C. ^¹H NMR (500 MHz, CDCl₃): δ = 7.50 (d, J = 7.5 Hz, 1 H), 7.38 (d, J = 8.0 Hz, 1 H), 7.12-7.27 (m, 5 H), 7.03 (d, J = 7.5 Hz, 1 H), 4.63 (d, J = 4.5 Hz, 1 H), 3.56 (dd, J = 16.0, 4.5 Hz, 1 H), 3.50 (s, 3 H), 3.13 (d, J = 16.0 Hz, 1 H), 2.86 (m, 1 H), 2.71 (m, 1 H), 1.30 (t, J = 7.0 Hz, 3 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 137.4 (C), 137.0 (C), 133.4 (C), 129.5 (CH), 129.4 (CH), 127.8 (CH), 127.7 (CH), 127.6 (C) 126.1 (CH), 120.4 (CH), 119.3 (CH), 116.4 (CH), 108.5 (CH), 102.1 (C), 70.0 (CH), 50.8 (CH), 47.81 (CH₂), 36.7 (CH₂), 29.7 (CH₃), 13.1 (CH₃). Anal. Calcd for C₂₀H₂₀N₂S; C, 74.92; H, 6.29; N, 8.74. Found: C, 75.10; H, 6.48; N, 8.88.

5,14-Diethyl-5,7,12,13-tetrahydro-7,13-epimino[2]-benzothiocino[3,4- b ]indole (3k)
Pale yellow solid; mp 151-153 ˚C. ^¹H NMR (500 MHz, CDCl₃): δ = 7.54 (d, J = 7.5 Hz, 1 H), 7.39 (d, J = 7.5 Hz, 1 H), 7.31 (d, J = 7.5 Hz, 1H), 7.13-7.22 (m, 4 H), 7.05 (d, J = 7.5 Hz, 1 H), 4.65 (d, J = 5.0 Hz, 1 H), 4.02 (m, 2 H), 3.58 (dd, J = 15.5, 5.0 Hz, 1 H), 3.16 (d, J = 15.5 Hz, 1 H), 2.89 (m, 1 H), 2.73 (m, 1 H), 1.33 (t, J = 7.0 Hz, 3 H), 1.31 (t, J = 7.0 Hz, 3 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 137.5 (C), 136.0 (C), 133.4 (C), 129.6 (CH), 128.6 (C), 127.89 (C), 127.83 (CH), 127.74 (CH) 126.1 (CH), 120.4 (CH), 119.27 (CH), 116.59 (CH), 108.6 (CH), 102.2 (C), 69.8 (CH), 50.8 (CH), 47.8 (CH₂), 38.4 (CH₂), 36.7 (CH₂), 15.4 (CH₃), 13.1 (CH₃). Anal. Calcd for C₂₁H₂₂N₂S: C, 75.41; H, 6.63; N, 8.38. Found: C, 75.84; H, 6.57; N, 8.29.
14-Allyl-5-methyl-5,7,12,13-tetrahydro-7,13-epimino-[2]benzothiocino[3,4- b ]indole (3l)
White solid; mp 167-169 ˚C. ^¹H NMR (500 MHz, CDCl₃): δ = 7.51 (d, J = 7.5 Hz, 1 H), 7.38 (d, J = 7.5 Hz, 1 H), 7.29 (d, J = 7.5 Hz, 1 H), 7.13-7.23 (m, 4 H), 7.05 (d, J = 7.5 Hz, 1 H), 6.05 (m, 1 H), 5.87 (s, 1 H), 5.41 (d, J = 17.0 Hz, 1 H), 5.32 (d, J = 10.0 Hz, 1 H), 4.64 (d, J = 4.5 Hz, 1 H), 3.61 (dd, J = 15.5, 4.5 Hz, 1 H), 3.57 (s, 3 H), 3.48 (dd, J = 14.0, 6.0 Hz, 1 H), 3.30 (dd, J = 14.0, 6.0 Hz, 1 H), 3.15 (d, J = 16.0 Hz, 1 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 137.4 (C), 137.1 (C), 134.9 (CH), 133.4 (C), 129.6 (CH), 129.2 (C), 127.9 (CH), 127.7 (CH), 127.5 (C) 126.1 (CH), 120.5 (CH), 119.4 (CH), 119.3 (C), 116.6 (CH), 108.6 (C), 102.16 (CH₂), 69.8 (CH), 56.8 (CH₂), 50.9 (CH), 36.7 (CH₂), 29.8 (CH₃). Anal. Calcd for C₂₁H₂₀N₂S: C, 75.87; H, 6.06; N, 8.43. Found: C, 75.92; H, 6.14; N, 8.52.