NHC-Catalyzed Chemo- and Regioselective Hydrosilylation of Carbonyl Derivatives

Abstract

The hydrosilylation of carbonyl derivatives has been explored by the activation of diphenylsilane in the presence of a catalytic amount of an N-heterocyclic carbene (NHC). Presumably, a hypervalent silicon intermediate featuring strong Lewis acid character allows dual activation of both the carbonyl moiety and the hydride at the silicon center. Reduction under mild conditions could be accomplished using this organocatalytic process. Some interesting selectivities have been encountered.

Key words

hydrosilylation - N-heterocyclic carbenes - organocatalysis - reduction - green chemistry

References

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1

Present address: Institut de Chimie des Substances Naturelles CNRS, Avenue de la Terrasse, 91198 Gif-sur-Yvette Cedex, France

8

Hydrosilylation of ketone and imine with poly-NHC particles was reported recently, see ref. 7d.

17

The triazolium chloride salt (24.4 mg, 0.1equiv) was added to a suspension of NaH (60% in mineral oil, 4 mg, 0.1 equiv) in anhydrous DMF (1 mL) at r.t. After stirring for 30 min, H₂SiPh₂ (111 mg, 0.6 equiv) and the substrate (1 mmol) dissolved in anhydrous DMF (1 mL) were added to the reaction mixture. When no more substrate was seen by TLC analysis, TBAF (1.0 M in THF, 1 mL, 1 equiv) was added to the solution. Stirring was continued for 30 min and quenching was achieved with H₂O (10 mL). The mixture was extracted with EtOAc (3 × 10 mL) and the combined organic layers were washed with brine (10 mL), dried with anhydrous Na₂SO₄, filtered, and the solution was concen-trated in vacuo. The crude product was purified by flash chromatography.
Analytical data for some typical examples: Compound 2c: ^¹H NMR (400 MHz, CDCl₃): δ = 7.61 (d, J = 8.0 Hz, 2 H), 7.47 (q, J = 8.0 Hz, 2 H), 4.93 (q, J = 6.0 Hz, 1 H), 2.31 (br s, 3 H), 1.47 (d, J = 6.8 Hz, 3 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 151.2, 132.3, 126.1, 118.9, 111.0, 70.0, 25.4. Compound 2d: ^¹H NMR (400 MHz, CDCl₃): δ = 7.97 (d, J = 8.0 Hz, 2 H), 7.40 (q, J = 8.0 Hz, 2 H), 4.92 (q, J = 6.4 Hz, 1 H), 3.88 (s, 3 H), 2.49 (br s, 1 H), 1.47 (d, J = 6.4 Hz, 3 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 167.1, 151.1, 129.8, 129.1, 125.3, 69.9, 52.1, 25.3. Compound 2h: ^¹H NMR (400 MHz, CDCl₃): δ = 7.42 (d, J = 5.6 Hz, 1 H), 7.29-7.22 (m, 3 H), 5.24 (t, J = 6.0 Hz, 1 H), 3.06 (m, 1 H), 2.82 (m, 1 H), 2.53-2.44 (m, 1 H), 1.99-1.90 (m, 2 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 145.0, 143.3, 128.3, 126.7, 124.9, 124.2, 76.4, 35.9, 29.8. Compound 2j (syn/anti, 2.5:1): ^¹H NMR (400 MHz, CDCl₃): δ = 7.50-7.27 (m, 20 H, syn and anti), 5.00 (t, J = 2.0 Hz, 1 H, anti), 4.73 (t, J = 4.2 Hz, 1 H, syn), 4.17 (d, J = 2.0 Hz, 1 H, anti), 4.04 (d, J = 2.0 Hz, 1 H, syn), 3.34 (dd, J = 4.2, 2.0 Hz, 1 H, syn), 3.32 (dd, J = 2.8, 2.0 Hz, 1 H, anti), 3.01 (d, J = 4.2 Hz, 1 H, syn), 2.85 (d, J = 2.4 Hz, 1 H, anti). ^¹³C NMR (100 MHz, CDCl₃): δ = 140.2 (syn), 139.4 (anti), 136.6 (anti), 136.4 (syn), 128.8 (syn), 128.7 (anti), 128.6 (syn and anti), 128.5 (syn), 128.4 (anti), 128.3 (syn and anti), 126.7 (anti), 126.3 (syn), 125.8 (syn and anti), 73.5 (syn), 71.3 (anti), 65.9 (syn), 65.1 (anti), 57.0(syn), 55.2 (anti). Compound 2l: ^¹H NMR (400 MHz, CDCl₃): δ = 3.54 (m, 1 H), 1.84-1.67 (m, 5 H), 1.30-0.91 (m, 10 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 72.4, 45.1, 28.7, 28.4, 26.5, 26.2, 26.1, 20.4. Compound 4: ^¹H NMR (400 MHz, CDCl₃): δ = 7.35-7.24 (m, 5 H), 4.90 (br s, 1 H), 4.31 (d, J = 4.8 Hz, 2 H), 1.47 (s, 9 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 155.9, 139.0, 128.6, 127.5, 127.3, 79.5, 44.7, 28.4. Compound 6: ^¹H NMR (400 MHz, CDCl₃): δ = 6.04 (d, J = 16.0 Hz, 1 H), 5.48 (dd, J = 16.0, 6.8 Hz, 1 H), 4.35 (sext., J = 6.4 Hz, 1 H), 1.97 (t, J = 6.4 Hz, 2 H), 1.66 (s, 3 H), 1.62-1.51 (m, 3 H), 1.44 (m, 2 H), 1.32 (d, J = 6.0 Hz, 3 H), 0.98 (s, 6 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 137.6, 136.6, 128.8, 127.5, 69.5, 39.4, 33.9, 32.7, 28.7, 28.6, 23.6, 21.3, 19.2. Compound 12: ^¹H NMR (400 MHz, CDCl₃): δ = 7.40-7.26 (m, 5 H), 4.1 (s, 1 H), 3.74 (d, J = 11.6 Hz, 2 H), 3.19 (d, J = 11.6 Hz, 1 H), 2.92 (br s, 1 H), 0.73-0.62 (m, 3 H), 0.48-0.44 (m, 1 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 142.1, 128.2, 127.5, 126.2, 79.7, 68.4, 27.5, 9.8, 8.0.