Organometallics
Article
solvent, the crude mixture was purified by silica gel column
chromatography to afford 2a (1.990 g, 93% yield).
3-((Hydroxydimethylsilyl)oxy)-1,1,5,5-tetramethyl-3-phenyltrisi-
1
loxane-1,5-diol (2t): H NMR (400 MHz, CDCl3) δ 7.70 (dd, J =
7.9, 1.4 Hz, 2H), 7.47−7.39 (m, 3H), 2.99 (s, 1H), 0.31 (s, 6H), 0.23
(s, 12H); 13C NMR (100 MHz, CDCl3) δ 133.8, 133.0, 130.3, 127.9,
1.0, 0.7, 0.2.
Procedure for the One-Pot Silane Oxidation and Carbonyl
Reduction. In a 10 mL Schlenk tube were introduced organosilane
(1.0 mmol), iridium catalyst TC-6 (0.6 mg, 0.l mmol %), THF (0.25
mL), carbonyl compound, and H2O (2 mL). The reaction mixture
was stirred at room temperature until the completion of the reaction.
The mixture was extracted with diethyl ether (3 × 20 mL). The
combined diethyl ether layers were then dried over sodium sulfate and
concentrated under vacuum. After evaporation of the solvent, the
crude mixture was purified by silica gel column chromatography to
afford silanol and alcohol products.
Methoxymethyldiphenylsilane (4a): 1H NMR (400 MHz, CDCl3)
δ 7.60−7.58 (m, 4H), 7.40−7.34 (m, 6H), 3.53 (s, 3H), 0.63 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 135.8, 134.4, 130.0, 128.0, 51.3,
−3.5.
Methoxytriphenylsilane (4b): 1H NMR (400 MHz, CDCl3) δ 7.63
(dd, J = 7.8, 1.6 Hz, 6H), 7.36−7.30 (m, 9H), 3.61 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ 135.6, 134.2, 130.3, 128.2, 52.0.
Methyldiphenylsilanol (2a): 1H NMR (400 MHz, CDCl3) δ
7.56−7.51 (m, 4H), 7.38−7.27 (m, 6H), 3.52 (s, 1H), 0.55 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 137.2, 134.1, 129.9, 128.0, −1.2.
1
Ethoxytriphenylsilane (4c): H NMR (400 MHz, CDCl3) δ 7.63
(dd, J = 7.8, 1.5 Hz, 6H), 7.41−7.36 (m, 9H), 3.87 (q, J = 6.9 Hz,
2H), 1.23 (t, J = 7.0 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 135.5,
134.5, 130.0, 127.9, 59.8, 18.5.
1
tert-Butyldiphenylsilanol (2b): H NMR (400 MHz, CDCl3) δ
7.68 (dd, J = 7.9, 1.6 Hz, 4H), 7.35−7.28 (m, 6H), 2.76 (s, 1H), 1.04
(s, 9H); 13C NMR (100 MHz, CDCl3) δ 135.3, 135.0, 129.8, 127.9,
26.7, 19.1.
Triphenylpropoxysilane (4d): 1H NMR (400 MHz, CDCl3) δ
7.64−7.62 (m, 6H), 7.40−7.34 (m, 9H), 3.76 (dd, J = 7.3, 5.9 Hz,
2H), 1.61 (td, J = 7.3, 3.7 Hz, 2H), 0.90 (td, J = 7.4, 1.4 Hz, 3H); 13C
NMR (100 MHz, CDCl3) δ 135.5, 134.6, 130.0, 127.9, 65.7, 25.9,
10.5.
Triphenylsilane (2c): 1H NMR (400 MHz, CDCl3) δ 7.54 (dd, J =
8.0, 1.3 Hz, 6H), 7.39−7.34 (m, 3H), 7.28 (t, J = 7.3 Hz, 6H), 3.56 (s,
1H); 13C NMR (100 MHz, CDCl3) δ 135.2, 135.2, 130.2, 128.0.
Dimethylphenylsilanol (2d): 1H NMR (400 MHz, CDCl3) δ
7.49−7.45 (m, 2H), 7.31−7.23 (m, 3H), 3.14 (s, 1H), 0.26 (s, 6H);
13C NMR (100 MHz, CDCl3) δ 139.2, 133.2, 129.6, 127.9, 0.
(3,5-Bis(trifluoromethyl)phenyl)dimethylsilanol (2e): 1H NMR
(400 MHz, CDCl3) δ 8.02 (br, 2H), 7.91 (br, 1H), 3.07 (s, 1H), 0.46
(s, 6H); 13C NMR (100 MHz, CDCl3) δ 142.4, 132.9, 131.0, 130.7,
124.9, 123.3, 122.2, −0.2.
Benzylbutoxydimethylsilane (4e): 1H NMR (400 MHz, CDCl3) δ
7.23 (d, J = 7.6 Hz, 2H), 7.10−7.07 (m,3H), 3.60 (t, J = 6.6 Hz, 2H),
2.21 (s, 2H), 1.54−1.50 (m, 2H), 1.38- 1.31 (m, 2H), 0.93 (t, J = 7.3
Hz, 3H), 0.11 (s, 6H); 13C NMR (100 MHz, CDCl3) δ 139.2, 128.4,
128.2, 124.1, 62.8, 34.8, 26.7, 19.0, 13.9, −2.4.
1
Butoxymethyldiphenylsilane (4f): H NMR (400 MHz, CDCl3)
δ7.68−7.66 (m, 4H), 7.47−7.44 (m, 6H), 3.79−3.76 (m, 2H), 1.65−
1.62 (m, 2H), 1.46−1.43 (m, 2H), 0.97−0.95 (m, 3H), 0.73−0.71
(m, 3H); 13C NMR (100 MHz, CDCl3) δ 136.4, 134.4, 129.8, 127.9,
63.3, 34.8, 19.0, 13.9, −3.0.
1
Benzyldimethylsilanol (2f): H NMR (400 MHz, CDCl3) δ 7.23
(d, J = 7.6 Hz, 2H), 7.12−7.05 (m, 3H), 2.18 (s, 2H), 0.14 (s, 6H);
13C NMR (100 MHz, CDCl3) δ 139.2, 128.5, 128.3, 124.3, 28.2,
−0.7.
Butoxytriphenylsilane (4g): 1H NMR (400 MHz, CDCl3) δ 7.64−
7.62 (m, 6H), 7.39−7.33 (m, 9H), 3.80 (t, J = 6.5 Hz, 2H), 1.57−
1.55 (m, 2H), 1.38−1.35 (m, 2H), 0.85 (t, J = 7.4 Hz, 3H); 13C NMR
(100 MHz, CDCl3) δ 135.5, 134.7, 130.1, 128.0, 63.8, 34.8, 19.1, 14.0.
Isopropoxymethyldiphenylsilane (4h): 1H NMR (400 MHz,
CDCl3) δ 7.61−7.59 (m, 4H), 7.38−7.34 (m, 6H), 4.09 (dt, J =
12.1, 6.1 Hz, 1H), 1.17 (d, J = 6.1 Hz, 6H), 0.65 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ 136.9, 134.4 129.7, 127.8, 65.9, 25.8, −2.3.
1
tert-Butyldimethylsilanol (2g): H NMR (400 MHz, CDCl3) δ
3.63 (s, 1H), 0.91 (s, 9H), 0.03 (d, J = 3.7 Hz, 6H); 13C NMR (100
MHz, CDCl3) δ 26.7, −6.9.
Triethylsilanol (2h): 1H NMR (400 MHz, CDCl3) δ 3.61 (s, 1H),
0.98 (t, J = 7.9 Hz, 9H), 0.62−0.55 (m, 6H); 13C NMR (100 MHz,
CDCl3) δ 8.1, 2.5.
1
1
Isopropoxytriphenylsilane (4i): H NMR (400 MHz, CDCl3) δ
Tributylsilanol (2i): H NMR (400 MHz, CDCl3) δ 1.49 (s, 1H),
7.65−7.62 (m, 6H), 7.41−7.33 (m, 9H), 4.18 (dt, J = 12.1, 6.0 Hz,
1H), 1.18 (d, J = 6.1 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 135.5,
135.1, 129.9, 127.8, 66.4, 25.8.
1.35−1.31 (m, 12H), 0.89 (t, J = 7.0 Hz, 9H), 0.62−0.58 (m, 6H);
13C NMR (100 MHz, CDCl3) δ 26.6, 25.3, 14.8, 13.8.
Trihexylsilanol (2j): 1H NMR (400 MHz, CDCl3) δ 1.33−1.25 (m,
25H), 0.88 (t, J = 6.9 Hz, 9H), 0.60−0.56 (m, 5H); 13C NMR (100
MHz, CDCl3) δ 33.3, 31.6, 23.1, 22.6, 15.1, 14.1.
1
Dimethoxydiphenylsilane (4j): H NMR (400 MHz, CDCl3) δ
7.67−7.64 (m, 4H), 7.43−7.38 (m, 6H), 3.63 (s, 6H); 13C NMR
(100 MHz, CDCl3) δ 134.8, 132.2, 130.4, 127.9, 51.0.
Methyldiphenylsilane (1a): 1H NMR (400 MHz, CDCl3) δ 7.56−
7.54 (m, 4H), 7.38−7.33 (m, 6H), 4.94 (q, J = 3.8 Hz, 1H), 0.61 (d, J
= 3.8 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 135.4, 134.9, 129.6,
128.1, −4.9.
1
Triisopropylsilanol (2k): H NMR (400 MHz, CDCl3) δ 1.59 (br,
18H), 1.28 (br, 3H); 13C NMR (100 MHz, CDCl3) δ 19.4, 10.2.
1
Tri-tert-butylsilanol (2l): H NMR (400 MHz, CDCl3) δ 3.34 (s,
1H), 1.09 (s, 27H); 13C NMR (100 MHz, CDCl3) δ 19.5, 10.3.
1
Tris(trimethylsilyl)silanol (2m): H NMR (400 MHz, CDCl3) δ
1.32 (s, 1H), 0.23 (s, 27H); 13C NMR (100 MHz, CDCl3) δ −0.7.
3-((Dimethylsilyl)oxy)-1,1,5,5-tetramethyl-3-phenyltrisiloxane
1
(1t): H NMR (400 MHz, CDCl3) δ 7.58−7.56 (m, 2H), 7.41−7.35
1
Triethoxylsilanol (2n): H NMR (400 MHz, CDCl3) δ 4.29 (s,
(m, 3H), 4.77 (dd, J = 5.5, 2.7 Hz, 3H), 0.22 (d, J = 2.8 Hz, 19H);
1H), 3.86 (q, J = 7.0 Hz, 6H), 1.25 (t, J = 7.0 Hz, 9H); 13C NMR
(100 MHz, CDCl3) δ 58.3, 18.1.
13C NMR (100 MHz, CDCl3) δ 134.0, 133.8, 129.9, 127.7, 0.5.
1
Tris(trimethylsiloxyl)silanol (2o): H NMR (400 MHz, CDCl3) δ
4.26 (s, 1H), 0.15 (s, 27H); 13C NMR (100 MHz, CDCl3) δ 1.7.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
■
1
Methylphenylvinylsilanol (2p): H NMR (400 MHz, CDCl3) δ
S
7.65−7.64 (m, 2H), 7.47−7.41 (m, 3H), 6.37−6.18 (m, 2H), 6.02−
5.94 (m, 1H), 0.77−0.74 (m, 3H); 13C NMR (100 MHz, CDCl3) δ
136.0, 134.5, 134.3, 133.7, 130.6, 128.2, 0.4.
1
Dimethylvinylsilanol (2q): H NMR (400 MHz, CDCl3) δ 6.25−
NMR spectra for all products (PDF)
6.06 (m, 2H), 5.89 (dd, J = 19.8, 3.6 Hz, 1H), 0.5 (s, 6H); 13C NMR
(100 MHz, CDCl3) δ 136.1, 134.1, 1.6.
AUTHOR INFORMATION
Corresponding Author
1
Diphenylsilanediol (2r): H NMR (400 MHz, CD3OD) δ 7.67
■
(dd, J = 7.8, 1.6 Hz, 4H), 7.40−7.33 (m, 6H); 13C NMR (100 MHz,
CD3OD) δ 136.1, 134.0, 129.4, 127.2.
Si,Si,Si′,Si′-Tetramethylbenzene-1,2-bis(silanol) (2s): 1H NMR
(400 MHz, CDCl3) δ 7.57−7.52 (m, 4H), 2.02 (s, 2H), 0.37 (d, J
= 28.4 Hz, 12H); 13C NMR (100 MHz, CDCl3) δ 144.4, 134.4, 128.5,
−2.5, −2.8.
ORCID
E
Organometallics XXXX, XXX, XXX−XXX