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DOI: 10.1055/s-2007-980343
Silylation of Aryl Iodides with 1,1,1,3,5,5,5-Heptamethyltrisiloxane Catalyzed by Transition-Metal Complexes
Publication History
Publication Date:
23 May 2007 (online)
Abstract
The silylation of various kinds of aryl iodides with 1,1,1,3,5,5,5-heptamethyltrisiloxane was achieved by a suitable transition-metal catalyst, such as Pd(0), Pt(0), and Rh(I). These catalytic systems showed dramatically different substrate scope.
Key words
silicon - transition metals - catalysis - cross-coupling - aryl halides
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References and Notes
1,1,1,3,5,5,5-Heptamethyltrisiloxane (1) is commercially available.
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Silylation of Aryl Iodides; General Procedure: In a glove box, the appropriate transition-metal complex (0.015 mmol) and KOAc (1.5 mmol) were placed in a screw-capped vial. NMP (2 mL), aryl iodide 2 (0.5 mmol), and 1,1,1,3,5,5,5-heptamethyltrisiloxane (1; 1.0 mmol) were added successively. The vial was sealed with a cap and removed from the glove box. The reaction mixture was then stirred at r.t. for 16 h. After the reaction was completed, the mixture was diluted with Et2O, washed with H2O (3 ×) to remove NMP, and dried over Na2SO4. The solvent was removed under reduced pressure, and the residue was purified by Kugelrohr distillation to give the desired 3-aryl-1,1,1,3,5,5,5-heptamethyltrisiloxane 3. The products were characterized by 1H and 13C NMR spectroscopy and HRMS analysis.
3a: 1H NMR (CDCl3): δ = 0.10 (s, 18 H), 0.24 (s, 3 H), 3.82 (s, 3 H), 6.90 (d, J = 8.2 Hz, 2 H), 7.48 (d, J = 8.2 Hz, 2 H). 13C NMR (CDCl3): δ = 0.16, 1.85, 54.97, 113.25, 129.25, 134.75, 160.62. HRMS (EI): m/z [M+] calcd for C14H28O3Si3: 328.1347; found: 328.1350. 3b: 1H NMR (CDCl3): δ = 0.10 (s, 18 H), 0.29 (s, 3 H), 1.40 (t, J = 7.2 Hz, 3 H), 4.38 (q, J = 7.2 Hz, 2 H), 7.62 (d, J = 7.9 Hz, 2 H), 8.01 (d, J = 7.9 Hz, 2 H). 13C NMR (CDCl3): δ = -0.15, 1.81, 14.32, 60.91, 128.43, 131.15, 133.13, 144.22, 166.79. HRMS (EI): m/z [M+ - CH3] calcd for C15H27O4Si3: 355.1217; found: 355.1220. 3c: 1H NMR (CDCl3): δ = 0.09 (s, 18 H), 0.27 (s, 3 H), 3.79 (s, 3 H), 6.81 (d, J = 7.6 Hz, 1 H), 6.94 (t, J = 7.6 Hz, 1 H), 7.35 (t, J = 7.6 Hz, 1 H), 7.50 (d, J = 7.6 Hz, 1 H). 13C NMR (CDCl3): δ = 1.06, 1.78, 54.58, 109.18, 120.18, 126.00, 131.24, 135.45, 164.00. HRMS (EI): m/z [M+] calcd for C14H28O3Si3: 328.1346; found: 328.1384. 3d: 1H NMR (CDCl3): δ = 0.12 (s, 18 H), 0.28 (s, 3 H), 7.30-7.60 (m, 5 H). 13C NMR (CDCl3): δ = 0.02, 1.85, 127.58, 129.39, 133.21, 138.52. HRMS (EI): m/z [M+] calcd for C13H26O2Si3: 298.1241; found: 298.1282. 3e: 1H NMR (CDCl3): δ = 0.10 (s, 18 H), 0.24 (s, 3 H), 4.91 (s, 1 H), 6.82 (d, J = 8.2 Hz, 2 H), 7.43 (d, J = 8.2 Hz, 2 H). 13C NMR (CDCl3): δ = 0.12, 1.83, 114.68, 129.82, 135.01, 156.81. HRMS (EI): m/z [M+] calcd for C13H26O3Si3: 314.1190; found: 314.1179. 3f: 1H NMR (CDCl3): δ = 0.09 (s, 18 H), 0.22 (s, 3 H), 3.72 (br s, 2 H), 6.67 (d, J = 8.5 Hz, 2 H), 7.34 (d, J = 8.5 Hz, 2 H). 13C NMR (CDCl3): δ = 0.17, 1.86, 114.27, 126.99, 134.61, 147.52. HRMS (EI): m/z [M+] calcd for C13H27O2NSi3: 313.1350; found: 313.1317. 3g: 1H NMR (CDCl3): δ = 0.11 (s, 18 H), 0.32 (s, 3 H), 7.17 (t, J = 4.0 Hz, 1 H), 7.31 (d, J = 4.0 Hz, 1 H), 7.57 (d, J = 4.0 Hz, 1 H). 13C NMR (CDCl3): δ = 1.11, 1.77, 127.79, 130.42, 134.46, 138.05. HRMS (EI): m/z [M+] calcd for C11H24O2SSi3: 304.0805; found: 304.0807. 3h: 1H NMR (CDCl3): δ = 0.11 (s, 18 H), 0.29 (s, 3 H), 2.61 (s, 3 H), 7.65 (d, J = 7.9 Hz, 2 H), 7.29 (d, J = 7.9 Hz, 2 H). 13C NMR (CDCl3): δ = -0.14, 1.82, 26.63, 127.19, 133.39, 137.69, 144.68, 198.46. HRMS (EI): m/z [M+ - CH3] calcd for C14H25O3Si3: 325.1111; found: 325.1127. 3i: 1H NMR (CDCl3): δ = 0.12 (s, 18 H), 0.29 (s, 3 H), 7.45 (t, J = 7.6 Hz, 1 H), 7.66 (d, J = 7.6 Hz, 1 H), 7.75 (d, J = 7.6 Hz, 1 H), 7.80 (s, 1 H). 13C NMR (CDCl3): δ = -0.21, 1.80, 111.92, 119.25, 128.22, 132.78, 136.83, 137.24, 140.48. HRMS (EI): m/z [M+ - CH3] calcd for C13H22O2NSi3: 308.0959; found: 308.0937. 3j: 1H NMR (CDCl3): δ = 0.11 (s, 18 H), 0.28 (s, 3 H), 7.59 (d, J = 7.9 Hz, 2 H), 7.66 (d, J = 7.9 Hz, 2 H). 13C NMR (CDCl3): δ = -0.13, 1.79, 124.25 (q, J = 4.1 Hz), 124.33 (q, J = 272.1 Hz), 131.45 (q, J = 32.1 Hz), 133.54, 143.22. HRMS (EI): m/z [M+ - CH3] calcd for C13H22O2F3Si3: 351.0880; found: 351.0886. 3k: 1H NMR (CDCl3): δ = 0.12 (s, 18 H), 0.31 (s, 3 H), 7.71 (d, J = 8.2 Hz, 2 H), 8.19 (d, J = 8.2 Hz, 2 H). 13C NMR (CDCl3): δ = -0.19, 1.81, 117.26, 122.31, 134.09, 147.11. HRMS (EI): m/z [M+ - CH3] calcd for C12H22O4NSi3: 328.0856; found: 328.0866. 3l: 1H NMR (CDCl3): δ = 0.10 (s, 18 H), 0.25 (s, 3 H), 7.40 (d, J = 7.9 Hz, 2 H), 7.49 (d, J = 7.9 Hz, 2 H). 13C NMR (CDCl3): δ = -0.07, 1.82, 124.22, 130.78, 134.83, 137.30. HRMS (EI): m/z [M+ - CH3] calcd for C12H22O2BrSi3: 363.0090; found: 363.0068.