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DOI: 10.1055/s-0031-1290208
NHC-Catalyzed Chemo- and Regioselective Hydrosilylation of Carbonyl Derivatives
Publikationsverlauf
Publikationsdatum:
26. Januar 2012 (online)
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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
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References
Present address: Institut de Chimie des Substances Naturelles CNRS, Avenue de la Terrasse, 91198 Gif-sur-Yvette Cedex, France
8Hydrosilylation of ketone and imine with poly-NHC particles was reported recently, see ref. 7d.
17The 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.