Silylation of Aryl Iodides with 1,1,1,3,5,5,5-Heptamethyltrisiloxane Catalyzed by Transition-Metal Complexes

Miki Murata; Kosuke Ota; Hiroyuki Yamasaki; Shinji Watanabe; Yuzuru Masuda

doi:10.1055/s-2007-980343

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Synlett 2007(9): 1387-1390
DOI: 10.1055/s-2007-980343

LETTER

Silylation of Aryl Iodides with 1,1,1,3,5,5,5-Heptamethyltrisiloxane Catalyzed by Transition-Metal Complexes

Miki Murata*, Kosuke Ota, Hiroyuki Yamasaki, Shinji Watanabe, Yuzuru Masuda
Department of Materials Science, Kitami Institute of Technology, 165 Koencho, Kitami 090-8507, Japan
Fax: +81(157)264973; e-Mail: muratamk@mail.kitami-it.ac.jp;

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Publication History

Received 22 March 2007
Publication Date:
23 May 2007 (online)

Abstract
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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

References and Notes

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9

1,1,1,3,5,5,5-Heptamethyltrisiloxane (1) is commercially available.

14

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.