Synthesis of perfluoroalkylated carboranes by cross-metathesis of allylcarboranes and perfluoroalkylpropenes

Synlett

Volumn , Issue 6, 2010, Pages 885-888

  Eignerová, Barbara ^a,b   Janouek, Zbynk ^c   Draĉínský, Martin ^b   Kotora, Martin ^a,b  

^a CHARLES UNIVERSITY   (Czech Republic)

^b INSTITUTE OF ORGANIC CHEMISTRY AND BIOCHEMISTRY   (Czech Republic)

^c INSTITUTE OF INORGANIC CHEMISTRY   (Czech Republic)

Author keywords

Carboranes; Metallacarboranes; Metathesis; Perfluoroalkylation; Ruthenium

Indexed keywords

ALLYL COMPOUND; CARBORANE DERIVATIVE; PERFLUORO COMPOUND; PROPYLENE; RUTHENIUM COMPLEX;

ARTICLE; CATALYSIS; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; SYNTHESIS;

EID: 77949905929     PISSN: 09365214     EISSN: 14372096     Source Type: Journal    
DOI: 10.1055/s-0029-1219546     Document Type: Article

References (22)

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18. It has been recently shown that the cross-metathesis can be successfully carried out with allyl sulfides:, Lin Y A., Chalker J M., Floyd N, Bernades G J. L., Davis B G., [nl] J. Am. Chem. Soc. 2008 130 9642; and references therein
19. Seiser T, Kamena F, Cramer N, Angew. Chem. Int. Ed. 2008 47 6483
20. 1-(5,5,6,6,7,7,8,8,9,9,10,10,10-Tridecafluorodecen-2-en- 1-yl)-1,2-dicarbadodecaborane (7a) A solution of 2 (90 mg, 0.50 mmol) and 1a (360 mg, 1.00 mmol), HoveydaGrubbs second-generation catalyst (32 mg, 0.05 mmol) in CH2Cl2 (4 mL) was stirred at 42 C under Argon atmosphere for 4 h. Column chromatography on silica gel(heptane) afforded 7a (85 mg, 34%) as a colorless oil and the carborane homodimer 12a (20 mg, 23%) as a colorless oil. Compound 7a: 1H NMR (600 MHz CDCl3): d = 1.592.81 (m, 10 H, B-H), 2.87 (br td, J4,F = 18.0 Hz, J4,3 = 7.0 Hz, 2 H, H-4), 2.99 (dm, J1,2 = 7.4 Hz, 2 H, H-1), 3.52 (br s, 1 H, H-2), 5.55 (dtm, J3,2 = 15.3 Hz, J3,4 = 7.0 Hz, 1 H, H-3), 5.66 (dtt, J2,3 = 15.3 Hz, J2,1 = 7.4 Hz, J2,4 = 1.1 Hz, 1 H, H-2). 13C NMR (150.9 MHz, CDCl3): d = 34.77 (t, J4,F = 22.8 Hz, CH2-4), 40.52 (CH2-1), 59.69 (CH-2), 73.08 (C-1), 123.21 (t, J3,F = 4.4 Hz, CH-3), 131.40 (CH-2). 11B NMR (160.4 MHz, CDCl3, BF3OEt2): d = 1.35 (d, J = 150 Hz, 1 B, B-9), 4.70 (d, J = 150 Hz, 1 B, B-12), 8.23 (d, J = 153 Hz, 2 B, B-8 and B-10), 10.40 (d, J = 160 Hz, 2 B, B-4 and B-5), 11.80 (d, J = ca. 100 Hz, 2 B, B-7 and B-11), 12.10 (d, J = 155 Hz, 2 B, B-3 and B-6). 19F NMR (470.3 MHz, CDCl3, C6F6): d = 76.99 (m, 3 F), 109.17 (m, 2 F), 118.11 (m, 2 F), 119.07 (m, 2 F), 119.21 (m, 2 F), 122.33 (m, 2 F). IR (CHCl3): n = 3068, 2929, 2597, 1362, 1243, 1020, 997 cm1. ESI-MS: m/z (%) = 518 (8) [M+], 495 (100), 475 (45), 435 (17), 416 (5). ESI-HRMS: m/z calcd for C12H16B10F13 [M+H]: 517.1980; found: 517.1987. Rf = 0.63 (hexane). Compound 12a: 1H NMR (600 MHz, CDCl3): d = 3.15 (m, 4 H, H-1), 4.61 (br s, 2 H, H-2), 5.66 (m, 2 H, H-2). 13C NMR (150.9 MHz, CDCl3): d = 40.52 (2 C, CH2-1), 62.71 (2 C, CH-2), 75.68 (2 C, C-1), 130.45 (2 C, CH-2). 11B NMR (160.4 MHz, CDCl3, BF3OEt2): d = 2.07 (d, J = 151 Hz, 2 B, B-9), 5.21 (d, J = 150 Hz, 2 B, B-12), 8.71 (d, J = 153 Hz, 4 B, B-8 and B-10), 10.59 (d, J = 160 Hz, 4 B, B-4 and B-5), 11.41 (d, J = ca. 110 Hz, 4 B, B-7 and B-11), 12.21 (d, J = 158 Hz, 4 B, B-3 and B-6). IR (CHCl3): n = 3067, 2929, 2598, 1433, 1018, 979 cm1. MS (EI): m/z (%) = 344 (7) [M+], 181 (47), 153 (15). HRMS (EI): m/z calcd for C8H28B20 [M+]: 344.4052; found: 344.4068. Rf = 0.60 (hexane).
21. It has been recently shown that the cross-metathesis can be successfully carried out with allyl sulfides: (a) Lin, Y. A.; Chalker, J. M.; Floyd, N.; Bernades, G. J. L.; Davis, B. G. J. Am. Chem. Soc. 2008, 130, 9642
22. and references therein. (b) Seiser, T.; Kamena, F.; Cramer, N. Angew. Chem. Int. Ed. 2008, 47, 6483.