D. J. M. Snelders et al. / Tetrahedron: Asymmetry 21 (2010) 1411–1420
1419
1
6 h. The suspension was filtered over Celite and the filtrate was
dried in vacuo, redissolved in CH Cl , and filtered again over Celite.
The filtrate was dried in vacuo, yielding the product as a light yel-
low powder. Yield: 404 mg (quant.). 1H NMR (400 MHz, CD
CN/
CDCl , 1/1 (v/v)): d (ppm) = 8.1–7.9 (br m, 9H, o- and p-Ar), 7.4–
takes throughout the reactions. The stainless steel autoclaves of
the AMTEC SPR16 were flushed automatically with argon 6 times
to remove oxygen traces. The reactors were charged with a solu-
tion of the precatalyst under argon. The atmosphere was further
2
2
3
3
2
exchanged with a 1/1 mixture of CO/H (gas exchange cycle 1)
0
7
.1 (br m, 60H, Ph), 6.8–6.6 (br m, 18H, Ar ), 4.95 (br s, 24H,
and the reactors were heated and pressurized. In case of hydrofor-
mylation, the preformation of the catalyst under the applied condi-
tions (vide infra) was performed for 2 h. Subsequently, the
substrate was injected and the desired temperature and the final
pressure were adjusted and kept constant throughout the experi-
ment (Vtot = 8 mL). The uptake of synthesis gas was monitored
and recorded automatically. At the end of the catalysis experi-
ments, the reactors were cooled to room temperature and the
autoclave contents were analyzed by means of GC and chiral GC.
1
3
1
OCH
2
), 4.41 (br., 24H, NCH
CN/CDCl
P,C = 6.6 Hz, Trisphat), 136.6 (s, o-Ar ), 128.9 (s,
Ph), 128.5 (s, Ph), 128.0 (s, Ph), 123.0 (s, Trisphat), 114.2 (d,
2
), 2.93 (br s, 36H, N(CH
3 2
) ). C{ H}
NMR (101 MHz, CD
3
3
, 1/1 (v/v)): d (ppm) = 160.7 (s, m-
0
2
0
Ar ), 142.1 (d,
J
3
0
J
P,C = 19.5 Hz, Trisphat), 112.8 (s, p-Ar’), 104.1 (s, i-Ar ), 70.6 (s,
OCH ), 68.0 (br s, NCH ), 49.8 (s, N(CH ) (signals of Ar and i-Ph
not resolved). P{ H} NMR (162 MHz, CD CN/CDCl , 1/1 (v/v)): d
), ꢀ80.0 (Trisphat). Elem. Anal. Calcd for
(7036.69): C, 46.09; H, 2.45; Cl, 36.28; N,
.19; P, 3.08. Found: C, 45.65; H, 2.40; Cl, 36.25; N, 1.28; P, 2.85.
2
2
3 2
)
3
1
1
3
3
(
C
1
ppm) = ꢀ2.0 (PAr
3
270 6 48 7
H171Cl72N O P
5.12. Procedure for catalytic hydroformylation reactions
2
D
0
½
a
ꢁ
¼ ꢀ361 (c 0.17 mM in CH
2
Cl
2
, i.e., 1.0 mM
D
-Trisphat). CD (c
ꢀ5
ꢀ5
0
.83 ꢂ 10 M in MeCN, i.e., 5.0 ꢂ 10
M
D
-Trisphat, 2 mm quartz
Rh(acac)(CO)
2
(3.0 mg, 0.012 mmol) and phosphine ligand
Cl (6.0 mL
cuvette, 20 °C) k (
D
e
) = 244 (ꢀ62), 220 (ꢀ262), 211 (+214).
(0.023–0.047 mmol) were dissolved in MeCN or CH
2
2
for hydroformylation of styrene, 5.3 mL for hydroformylation of
1-octene) and stirred for 5 min at room temperature. The clear,
light green solutions were then transferred via syringe into the
AMTEC parallel autoclaves. Catalyst preformation was carried out
5
.9. [3][camphorsulfonate] 14
6
4 6 2 2
To a solution of [3][BF ] (0.55 g, 0.19 mmol) in CH Cl (100 mL)
was added a solution of ammonium camphorsulphonate (0.8 M in
demineralized water, 25 mL). The mixture was vigorously stirred
for 20 min. The layers were allowed to separate, the aqueous layer
was removed, and the procedure was repeated twice with a fresh
solution of ammonium camphorsulphonate. The organic layer
was subsequently washed with demineralized water (4 ꢂ 50 mL)
2
for 2 h at 50 °C under 20 bar CO/H . The substrate (for styrene,
2.0 mL (17 mmol), for 1-octene, 2.7 mL (17 mmol)) was subse-
quently added via syringe and the hydroformylation was carried
2
out for 24 h at 20 bar CO/H at 50 °C (styrene) or 80 °C (1-octene).
5.13. Procedure for catalytic hydrogenation reactions
and dried in vacuo, yielding the product as an off-white powder.
1
Yield: 0.58 g (82%). H NMR (400 MHz, CD
3
CN): d (ppm) = 8.12
[Rh(cod) ][BF ] (3.2 mg, 0.0079 mmol), phosphine ligand
2
4
3
(
d,
J
P,H = 6.8 Hz, 6H, o-Ar), 7.97 (s, 3H, p-Ar), 7.38–7.23 (m, 60H,
Ph), 6.89 (s, 12H, o-Ar ), 6.68 (s, 6H, p-Ar ), 5.03 (s, 24H, OCH
(0.016 mmol), and dimethyl itaconate (0.63 g, 4.0 mmol) were dis-
solved in MeCN or CH Cl (8.0 mL) and stirred for 5 min at room
0
0
2
),
2
2
0
4
J
6
.63 (s, 12H, NCH
2
Ar ), 4.53 (s, 12H, NCH
2
Ar), 3.01 (d, 6H,
), 2.92 (s, 36H, N(CH ), 2.63 (m,
H,H = 14.4 Hz, camph., CH SO ), 2.13
temperature. The clear, light green solutions were subsequently
transferred via syringe into the AMTEC parallel autoclaves. The
2
H,H = 14.8 Hz, camph., CH
H, camph.), 2.51 (d, 6H,
2
SO
J
3
3 2
)
2
2
3
hydrogenation was then carried out for 24 h at 10 bar H at 30 °C.
2
(
(
m, 6H, camph.), 1.89 (m, 6H, camph.), 1.79 (m, 6H, camph.), 1.68
d, 6H, JH,H = 18.0 Hz, camph.), 1.46 (m, 6H, camph.), 1.16 (m, 6H,
References
camph.), 0.93 (s, 18H, camph., CH
3
), 0.66 (s, 18H, camph., CH
3
).
1
3
1
C{ H} NMR (101 MHz, CD
3
CN): d (ppm) = 217.5 (s, camph., C@O),
1. Rhodium Catalyzed Hydroformylation; Van Leeuwen, P. W. N. M., Claver, C., Eds.;
Kluwer Academic: Dordrecht, 2000.
2. (a)Aqueous-Pase Organometallic Catalysis; Cornils, B., Herrmann, W. A., Eds.;
Wiley-VCH: Weinheim, 1998; (b)Catalysis: An Integrated Approach; Van Santen,
R. A., Van Leeuwen, P. W. N. M., Moulijn, J. A., Averill, B. A., Eds., 2nd ed.;
Elsevier: Amsterdam, 1999.
0
1
(
60.9 (s, m-Ar ), 141.3 (m, overlapping Ar), 140.0 (br s, Ar), 137.8
0
3
s, o-Ar ), 131.0 (s, i-Ph), 130.3 (d, JP,C = 7.0 Hz, m-Ar), 129.4 (s, Ph),
0
0
1
28.9 (s, Ph), 128.8 (s, Ph), 113.4 (s, p-Ar ), 104.7 (s, i-Ar ), 70.9 (s,
), 68.4 (s, NCH ), 68.1 (s, NCH ), 59.3 (s, camph.), 49.4 (s,
), 48.3 (s, camph.), 48.1 (s, camph.), 43.3 (s, camph.), 27.4
s, camph.), 25.6 (s, camph.), 20.4 (s, camph.), 20.2 (s, camph.).
OCH
3 2
N(CH )
2
2
2
3
4
.
.
Evans, D.; Osborn, J. A.; Wilkinson, G. J. Chem. Soc. A. 1968, 3133–3142.
(a) Herrmann, W. A.; Kohlpaintner, C. W. Angew. Chem., Int. Ed. 1993, 32, 1524–
(
1544; (b) Cornils, B.; Kuntz, E. G. J. Organomet. Chem. 1995, 502, 177–186.
3
1
1
P{ H} NMR (162 MHz, CD
3
CN): d (ppm) = -2.2. ESI MS: (m/z)
5. (a) Cornils, B.; Herrmann, W. A.; Horvath, I. T.; Leitner, W.; Mecking, S.; Olivier-
Bourbigou, H.; Vogt, D. Multiphase Homogeneous Catalysis; Wiley-VCH:
Weinheim, 2005; (b) Haumann, M.; Riisager, A. Chem. Rev. 2008, 108, 1474–
2+
3+
1
674.3 {[Mꢀ2camph.] , calcd 1674.3}, 1039.2 {[Mꢀ3camph.]
,
4+
calcd 1039.5}, 721.66 {[Mꢀ4camph.] , calcd 721.85}. Elem. Anal.
Calcd for C222 (3812.83): C, 69.93; H, 6.90; N, 2.20; P,
.81. Found: C, 70.10; H, 6.97; N, 2.23; P, 0.80.
1
497.
6. (a) Van Leeuwen, P. W. N. M.; Kamer, P. C. J.; Reek, J. N. H.; Dierkes, P. Chem. Rev.
000, 100, 2741–2769; (b) Kamer, P. C. J.; Van Leeuwen, P. W. N. M.; Reek, J. N.
261 6 6
H N O36PS
2
0
H. Acc. Chem. Res. 2001, 34, 895–904.
7
.
(a) Bourque, S. C.; Maltais, F.; Xiao, W.; Tardif, O.; Alper, H.; Arya, P.; Manzer, L.
E. J. Am. Chem. Soc. 1999, 121, 3035–3038; (b) Bourque, S. C.; Alper, H.; Manzer,
L. E.; Arya, P. J. Am. Chem. Soc. 2000, 122, 956–957; (c) Ropartz, L.; Morris, R. E.;
Foster, D. F.; Cole-Hamilton, C. J. Chem. Commun. 2001, 361–362; (d) Reek, J. N.
H.; De Groot, D.; Oosterom, G. E.; Kamer, P. C. J.; Van Leeuwen, P. W. N. M. Rev.
Mol. Biotech. 2002, 90, 159–181; (e) Oosterom, G. E.; Steffens, S.; Reek, J. N. H.;
Kamer, P. C. J.; Van Leeuwen, P. W. N. M. Top. Catal. 2002, 19, 61–73; (f) Huang,
Y.; Zhang, H.; Deng, G.; Tang, W.; Wang, X.; He, Y.; Fan, Q. J. Mol. Cat. A. 2005,
5
.10. Procedure for titration of [Rh(cod)
2 4 4 6
][BF ] with [1][BF ] ,
[
3][BF
4
]
6
and [5][BF
4 3
]
A solution of [Rh(cod)
2 4 3 3
][BF ] (5–10 mg) in CD CN/CH CN (2/8
(
v/v), 0.5 mL) was placed in an NMR tube. To this solution, portions
of 0.1 mL of a stock solution of phosphine ligand (1.0 equiv with re-
spect to Rh per 0.1 mL) were added via syringe, shaken at room
temperature for 1 min, and analyzed.
2
27, 91–96.
8. For reviews on dendritic catalysts, see for example: (a) Astruc, D.; Chardac, F.
Chem. Rev. 2001, 101, 2991–3023; (b) Oosterom, G. E.; Reek, J. N. H.; Kamer, P.
C. J.; Van Leeuwen, P. W. N. M. Angew. Chem., Int. Ed. 2001, 40, 1828–1849; (c)
Kreiter, R.; Kleij, A. W.; Klein Gebbink, R. J. M.; Van Koten, G. Top. Curr. Chem.
5
.11. General procedure for catalytic experiments in AMTEC
2001, 217, 163–199; (d) Van Heerbeek, R.; Kamer, P. C. J.; Van Leeuwen, P. W. N.
M.; Reek, J. N. H. Chem. Rev. 2002, 102, 3717–3756; (e) Helms, B.; Fréchet, J. M. J.
Adv. Synth. Catal. 2006, 348, 1125–1148; (f) Berger, A.; Klein Gebbink, R. J. M.;
Van Koten, G. Top. Organomet. Chem. 2006, 20, 1–38.
(a) Kreiter, R.; Klein Gebbink, R. J. M.; van Koten, G. Tetrahedron 2003, 59, 3989–
3997; (b) Snelders, D. J. M.; Kreiter, R.; Firet, J. J.; Van Koten, G.; Klein Gebbink,
Catalytic experiments were performed in the parallel reactor
system AMTEC SPR16, equipped with pressure sensors and a
mass-flow controller suitable for monitoring and recording gas up-
9.