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Synlett 2010(8): 1265-1267  
DOI: 10.1055/s-0029-1219803
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

An Efficient Synthesis of Carborane Amines via One-Step Reaction of Carborane Triflates with N-Nucleophiles

Valentina A. Ol’shevskaya*a, Yulia V. Dutikovaa,b, Andrei A. Tyutyunova, Elena G. Kononovaa, Pavel V. Petrovskiia, Dae D. Sungc, Valery N. Kalinina
a A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Street, 119991 Moscow, Russian Federation
Fax: +7(499)1356549; e-Mail: olshevsk@ineos.ac.ru;
b N. N. Blokhin Cancer Center, Russian Academy of Medical Sciences, 115478 Moscow, Russian Federation
c Department of Chemistry, Dong-A University, 604-714 Busan, Republic of Korea
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Publication History

Received 21 January 2010
Publication Date:
07 April 2010 (online)

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Abstract

1-Trifluoromethanesulfonylmethyl-o-carborane and cesium 1-trifluoromethanesulfonylmethyl-1-carba-closo-dodecaborate react with amines in refluxing acetonitrile in the presence of NaOAc without a catalyst to give the corresponding amino derivatives. This approach allows for simple synthesis of neutral and anionic carborane amines not readily available via other synthetic routes.

Key words

carboranes - triflates - N-nucleophiles - amino carboranes

    References and Notes

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11

General Procedure for the Synthesis of Amines 3a-e and 4a-c
A mixture of triflate 1 (1.0 g, 3.3 mmol), corresponding amine (3.3 mmol), and NaOAc (0.74 g, 9 mmol) in MeCN (10 mL) was refluxed for 4-8 h until the complete disap-pearance of 1 was proved by TLC (heptane-EtOAc, 7:3). Then the reaction mixture was poured into H2O (20 mL) and extracted with EtOAc (3 × 7 mL). The organic layers were combined, washed with H2O, and dried over MgSO4. Then the mixture was filtered, and the solvent was removed under reduced air pressure. The residue was chromatographed on SiO2 (eluent: heptane-EtOAc, 10:1) to afford the products as colorless solids.
Analytical Data for Compound 3a
Yield 76% (0.62 g); mp 92-93 ˚C. IR (KBr): 3392, 3069, 2595 cm-¹. ¹H NMR (400.13 MHz, CDCl3): δ = 1.52-2.90 (m, 10 H), 3.77 (s, 1 H), 3.92 (d, J = 6.5 Hz, 2 H), 4.03 (s, 1 H), 7.24-6.60 (m, 5 H). ¹¹B NMR (128.32 MHz, CDCl3): δ = -2.32 (d, J = 149 Hz, 1 B), -5.20 (d, J = 149 Hz, 1 B),
-9.11 (d, J = 150 Hz, 2 B), -11.47 (d, J = 169 Hz, 2 B),
-12.96 (d, J = 149 Hz, 4 B). Anal. Calcd (%) for C9H19B10N: C, 43.35; H, 7.63; N, 5.62. Found: C, 43.46; H, 7.81; N, 5.58.
Synthesis of Compound 5
To a stirred mixture of sodium amide prepared from sodium (0.16 g, 7.0 mmol) in liquid ammonia (50 mL), triflate 1 (2 g, 6.6 mmol) was added at -50 ˚C in anhyd toluene (10 mL). The reaction mixture was stirred at -50 ˚C for 1 h, then NH4Cl (0.37 g, 7 mmol) was slowly added. The liquid ammonia was evaporated and H2O (20 mL) was added. The product was extracted with EtOAc and dried over Na2SO4. The solvents were evaporated, and the crude product was purified by chromatography on SiO2 (eluent: heptane) to afford 0.95 g (84% yield) of 5. White solid; mp 158 ˚C. ¹H NMR (400.13 MHz, CDCl3): δ = 1.20-3.10 (m, 10 H), 2.80 (s, 2 H), 3.89 (s, 1 H), 4.06 (s, 2 H). ¹¹B NMR (128.32 MHz, CDCl3): δ = -2.66 (d, J = 148 Hz, 1 B), -4.94 (d, J = 149 Hz, 1 B), -9.04 (d, J = 150 Hz, 2 B), -11.79 (d, J = 164 Hz, 2 B), -13.10 (d, J = 165 Hz, 4 B). Anal. Calcd (%) for C3H15B10N: C, 20.81; H, 8.67; B, 62.43; N, 8.09. Found: C, 21.04; H, 8.57; B, 62.84; N, 8.15.

14

Synthesis of Compound 9 A mixture of triflate 2 (1.6 g, 3.6 mmol) and pyridine (0.28 g, 3.6 mmol) in CH2Cl2 (10 mL) was stirred at ambient temperature for 2 h. The solvent was removed to dryness in vacuo. The residue was washed with H2O (15 mL), filtered off, and dried in vacuo to afford 0.81 g (94%) of 9. ¹H NMR (400.13 MHz, CDCl3): d = 1.10-2.50 (m, 11 H), 3.60 (s, 2 H), 8.33 (dd, J = 5.6, 7.6 Hz, 2 H), 8.87 (t, J = 7.6 Hz, 1 H), 9.17 (d, J = 5.6 Hz, 1 H). Anal. Calcd (%) for C7H18B11N: C, 35.78; H, 7.67; B 50,60, N, 5.96. Found: C 35.22; H, 7.53; B, 51.02, N, 6.11.