I. Kownacki et al. / Applied Catalysis A: General 390 (2010) 94–101
95
toluene and 0.01945 g (0.025 mmol) of the catalyst [{Ir(-
OSiMe3)(cod)}2] were placed in a Schlenk’s flask under argon. Then
the solution was transferred by syringe into a glass ampoule, which
was placed in the pressure reactor flushed with argon prior to use.
The reactor was pressurized to 60 bar with CO. The reaction mixture
was magnetically stirred at 120 ◦C for 60 h. After this time the auto-
clave was allowed to cool to room temperature and the mixture was
analyzed on the GC. The solvent was removed under reduced pres-
sure and the product was isolated by fractional distillation under
vacuum or by preparative column chromatography.
Co2(CO)8
OSiR3
+
+
HSiR3
CO
Scheme 1. Cobalt catalyzed silylcarbonylation of olefins.
SiR'3
[Ir]
+
+
2 HSiR'3
CO
R
R
OSiR'3
Scheme 2. Iridium promoted conversion of olefins to enol silyl ethers of acylsilanes.
2.3.1. Compound 4-MeC6H4CH2CH C(OSiMe2Ph)SiMe2Ph (Entry
6)
2. Experimental
Yield 1.56 g (75%).
2.1. General methods and chemicals
Anal. calc. for C26H32OSi2 C 74.94; H 7.74; found C 75.00; H
7.87. 1H NMR (300 MHz, CDCl3, 300 K) ı(ppm) = 7.53 (m, 4H, m-
PhSiMe2–); 7.38 (m, 6H, o,p-PhSiMe2–); 7.11 (d, 2H, JH–H = 8.1 Hz,
4-MeC6H4–), 7.05 (d, 2H, JH–H = 8.1 Hz, 4-MeC6H4–); 5.70 (t, 1H,
JH–H = 8.1 Hz, –CH , Z-isomer), 5.33 (t, 1H, JH–H = 6.8 Hz, –CH , E-
isomer); 3.41 (d, 2H, JH–H = 6.8 Hz, –CH2–, E-isomer); 3.19 (d, 2H,
JH–H = 8.1 Hz, –CH2–, Z-isomer); 2.35 (s, 3H, 4-MeC6H4–, E-isomer);
2.33 (s, 3H, 4-MeC6H4–, Z-isomer); 0.46 (s, 6H, –OSiMe2Ph, Z-
isomer); 0.44 (s, 6H, –SiMe2Ph, Z-isomer), 0.35 (s, 6H, –SiMe2Ph,
E-isomer); 0.33 (s, 6H, –OSiMe2Ph, E-isomer); 13C NMR (75.42 MHz,
CDCl3, 300 K) ı(ppm) = 155.78; 138.24; 137.56; 135.44; 134.52;
134.24; 133.88; 133.66; 129.72; 129.38; 129.25; 129.12; 128.51;
128.22; 127.94; 126.05; 125.34; 33.23; 31.92; 21.27; −0.25;
−1.63; −2.78. 29Si NMR (59.59 MHz, C6D6, 300 K) ı(ppm) = 4.28
(–OSiMe2Ph); −12.40 (–SiMe2Ph).
20 mL glass vials). The tfb ligand [24] as well as the following
complexes [{Ir(-OSiMe3)(cod)}2] [25], [Ir(CO)2(PCy3)(OSiMe3)]
[7], [Ir(tfb)2Cl] [26], [{Ir(-OMe)(tfb)}2] [27], [{Ir(-OAc)(tfb)}2]
[28], [{Ir(-Cl)(tfb)}2] [29] and [Ir(CO)3(PCy3)(SiPh3)] [30] were
synthesized according to described methods. Column chromatog-
raphy was carried out with silica gel 60 from Fluka using
C6H12:tBuOMe = 49:1 or C6H14:AcOEt = 49:1. 1H, 13C and 29Si NMR
spectra were recorded on a Varian Gemini 300 VT spectrometer
and Varian Mercury 300 VT in C6D6. The mass spectra of the prod-
ucts and substrates were determined by GC/MS (Varian Saturn
2100T equipped with a DB-5, 30 m capillary column). GC analyses of
organic and organosilicon compounds were carried out on a Varian
CP-3800 series gas chromatograph with a capillary column DB-5,
30 m and TCD. Determination of gases was carried out on Varian
CP-3800 series gas chromatograph with a capillary column Varian
CarboPLOT P7, 25 m with post-column 2.5 m, and TCD detector. As
carrier gas argon was used. The chemicals were obtained from the
following sources: sodium trimethylsilanolate, C6D6, CDCl3 from
Aldrich Chemical Co., organosilicone reagents, styrene and sub-
stituted styrenes from Gelest Ltd., toluene, hexane, cyclohexane,
decane and other solvents from POCH Gliwice (Poland), carbon
monoxide (4.7) from Fluka. All solvents and liquid reagents were
dried and distilled under argon prior to use.
2.3.2. Compound 4-MeOC6H4CH2CH C(OSiMe2Ph)SiMe2Ph
(Entry 7)
Yield 1.56 g (72%).
Anal. calc. for C26H32O2Si2 C 72.17; H 7.45; found C 72.24; H
7.63. 1H NMR (300 MHz, C6D6, 300 K) ı(ppm) = 7.53 (m, 4H, m-
PhSiMe2–); 7.18 (m, 6H, o,p-PhSiMe2–); 7.04 (d, 2H, JH–H = 8.8 Hz,
4-MeOC6H4–), 6.74 (d, 2H, JH–H = 8.8 Hz, 4-MeOC6H4–); 5.82 (t, 1H,
JH–H = 7.8 Hz, –CH , Z-isomer), 5.44 (t, 1H, JH–H = 6.8 Hz, –CH , E-
isomer); 3.47 (d, 2H, JH–H = 6.8 Hz, –CH2–, E-isomer); 3.3 (s, 3H,
MeOC6H4–); 3.17 (d, 2H, JH–H = 7.8 Hz, –CH2–, Z-isomer); 0.31 (s, 6H,
–OSiMe2Ph); 0.30 (s, 6H, –SiMe2Ph); 13C NMR (75.42 MHz, C6D6,
300 K) ı(ppm) = 160.00; 158.49; 156.75; 155.81; 138.70; 137.53;
134.61; 134.33; 133.72; 133.41; 129.92; 129.51; 129.47; 129.17;
126.37; 125.35; 114.24; 54.73; 33.04; 31.70; −0.30; −0.54; −1.65;
−2.92 (SiCHMe2). 29Si NMR (59.59 MHz, C6D6, 300 K) ı(ppm) = 4.29
(–OSiMe2Ph); −12.43 (–SiMe2Ph).
2.2. General procedure for silylcarbonylation tests
Mixtures of the appropriate olefins RCH CH2 (5.0 mmol),
HSiMe2Ph (10 mmol), decane (internal standard, 5% of the sub-
strates volume) and 15 mL of dried and deoxygenated toluene with
the selected iridium(I) precursors (0.025 mmol) were prepared in
a Schlenk’s flasks under argon. The solutions obtained were placed
in 20 mL glass vials equipped with magnetic bars and perforated
aluminum caps under argon, and then glass reactors were placed
into the Parr pressure reactor (five reactors for one run). Then the
reactor was flushed with argon (5.0) and pressurized with CO (4.7).
The reaction mixture was magnetically stirred at a given temper-
ature for 60 h. After this time the pressure reactor was allowed to
cool to room temperature and the mixture was analyzed by the GC
and GC/MS methods. Conversion of the substrates was determined
using the internal standard calculation method. Yield of products
was calculated based on the conversion of HSiMe2Ph.
2.3.3. Compound 4-tBuOC6H4CH2CH C(OSiMe2Ph)SiMe2Ph
(Entry 8)
Yield 1.83 g (77%).
Anal. calc. for C29H38O2Si2 C 73.36; H 8.07; found 73.43; H
8.25. 1H NMR (400 MHz, CDCl3, 300 K) ı(ppm) = 7.52 (m, 4H, m-
PhSiMe2–); 7.36 (m, 6H, o,p-PhSiMe2–); 7.01 (d, 2H, JH–H = 8.3 Hz,
4-tBuOC6H4–), 6.91 (d, 2H, JH–H = 8.3 Hz, 4-tBuOC6H4–); 5.67 (t,
1H, JH–H = 8.0 Hz, –CH , Z-isomer), 5.33 (t, 1H, JH–H = 7.0 Hz, –CH
,
E-isomer); 3.39 (d, 2H, JH–H = 7.0 Hz, –CH2–, E-isomer); 3.15 (d,
2H, JH–H = 8.0 Hz, –CH2–, Z-isomer); 1.35 (s, 9H, 4-tBuOC6H4–,
E-isomer); 1.34 (s, 9H, 4-tBuOC6H4–, Z-isomer); 0.44 (s, 6H,
–SiMe2Ph, Z-isomer); 0.43 (s, 6H, –OSiMe2Ph, Z-isomer); 0.35 (s,
6H, –OSiMe2Ph, E-isomer); 0.31 (s, 6H, –SiMe2Ph, E-isomer). 13C
NMR (75.42 MHz, C6D6, 300 K) ı(ppm) = 155.81; 155.62; 138.46;
137.48; 136.03; 134.43; 134.14; 133.78; 133.63; 133.55; 133.16;
129.70; 129.63; 129.31; 129.23; 128.76; 128.51; 127.86; 125.85;
125.33; 124.28; 124.17; 78.25; 32.97; 31.48; 29.01; −0.34; −0.47;
−1.77; −2.84. 29Si NMR (59.59 MHz, C6D6, 300 K) ı(ppm) = 4.27
(–OSiMe2Ph); −12.41 (–SiMe2Ph).
2.3. Synthesis of silylcarbonylation products
RCH2CH C(OSiMe2Ph)SiMe2Ph (1a)
Portions of RCH CH2 (5.00 mmol) and HSiMe2Ph (1.43 g,
10.5 mmol) were dissolved in 15 mL of dried and deoxygenated