O. Saidi et al. / Tetrahedron Letters 49 (2008) 3516–3519
3519
3
1
1
C
C
51.6; P NMR (162 MHz, CDCl
3
) d 145.3; HRMS calcd for
P (M+H) : 323.0837. Found: 323.0841; Anal. Calcd for
P: C, 70.81; H, 4.69. Found: C, 70.73; H, 4.75.
After cooling with an ice bath for ca 15 min, the syngas was carefully
released and the resulting mixture was then passed through a small
column of silica. Conversion and selectivity were determined by
+
19
H
H
16
O
O
3
19
15
3
1
Ligand L2: H NMR (400 MHz, CDCl
.19 (t, J = 7.5 Hz, 2H), 7.30–7.40 (m, 6H), 7.50 (d, J = 7.5 Hz, 2H);
C NMR (100 MHz, CDCl
30.5, 131.5, 133.1, 149.3, 151.3; P NMR (162 MHz, CDCl
44.0; HRMS calcd for C18
86.9782; Anal. Calcd for C18
5.74; H, 3.01.
Ligand L3: H NMR (400 MHz, CDCl
H), 7.50 (d, J = 7.6 Hz, 2H), 7.96 (d, J = 7.6 Hz, 2H); C NMR
100 MHz, CDCl ) d 26.8, 120.6, 120.7, 122.4, 126.1, 129.7, 130.5,
30.7, 130.9, 131.4, 149.2, 156.3, 197.0; P NMR (162 MHz, CDCl
d 143.5; HRMS calcd for C20
51.0777; Anal. Calcd for C20
8.33; H, 4.41.
Ligand L4: H NMR (400 MHz, CDCl
.32 (t, J = 7.4 Hz, 2H), 7.37 (d, J = 7.5 Hz, 2H), 7.39–7.45 (m, 4H),
3
) d 7.06 (d, J = 7.5 Hz, 2H),
NMR. Only the branched product 2-N-phthalimidopropanal was
1
7
detected. H NMR (400 MHz, CDCl
3
) d 1.63 (d, J = 7.2 Hz, 3H),
1
3
3
) d 117.5, 122.5, 122.7, 126.0, 129.7,
4.75 (q, J = 7.2 Hz, 1H), 7.75–7.79 (m, 2H), 7.86–7.90 (m, 2H), 9.70
31
13
1
1
3
5
3
) d
13BrO P (M+H) : 386.9786. Found:
3
12BrO P: C, 55.84; H, 3.12. Found: C,
(s, 1H); C NMR (100 MHz, CDCl
168.0, 197.1; Anal. Calcd for C11
Found: C, 64.72; H, 4.40; N, 6.45.
3
) d 13.3, 54.5, 124.0, 132.2, 134.8,
+
H
3
H
9
NO
3
: C, 65.02; H, 4.46; N, 6.89.
H
1
Other branched products: 2-N-phthalimidobutanal from 2: H NMR
1
3
) d 2.58 (s, 3H), 7.21–7.40 (m,
3
(400 MHz, CDCl ) d 1.00 (t, J = 7.4 Hz, 3H), 2.06–2.31 (m, 2H),
1
3
8
(
1
4.58–4.64 (m, 1H), 7.74–7.80 (m, 2H), 7.86–7.91 (m, 2H), 9.72 (s, 1H);
1
3
3
C NMR (100 MHz, CDCl
168.3, 196.9; Anal. Calcd for C12
Found: C, 66.25; H, 5.10; N, 6.42.
2-(2-Oxopyrrolidin-1-yl)propanal from 3:
CDCl
J = 8.1 Hz, 2H), 3.30 (t, J = 7.0 Hz, 2H), 4.68 (q, J = 7.4 Hz, 1H),
3
) d 11.0, 21.0, 60.8, 124.0, 132.1, 134.7,
3
1
3
)
H11NO
3
: C, 66.35; H, 5.10; N, 6.45.
+
H O
16 4
P (M+H) : 351.0786. Found:
1
3
6
H
15
O
4
P: C, 68.57; H, 4.32. Found: C,
H NMR (400 MHz,
3
) d 1.15 (d, J = 7.4 Hz, 3H), 2.09–2.17 (m, 2H), 2.36 (t,
1
3
) d 7.19 (d, J = 8.0 Hz, 2H),
1
3
7
7
1
(
3
9.56 (s, 1H); C NMR (100 MHz, CDCl
56.5, 176.1, 199.5; Anal. Calcd for C 11NO
9.92. Found: C, 59.45; H, 7.90; N, 9.83.
3
) d 11.5, 18.6, 31.0, 43.6,
13
.49 (d, J = 7.5 Hz, 2H); C NMR (100 MHz, CDCl
24.5, 125.8, 126.2, 128.3, 129.7, 130.6, 131.1, 149.1, 152.5; P NMR
162 MHz CDCl
34.0633. Found: 334.0628; Anal. Calcd for C19
3
) d 114.1, 122.5,
7
H
2
: C, 59.56; H, 7.85; N,
3
1
+
1
3
) d 142.3; HRMS calcd for C19
H
13NO
3
P (M+H) :
P: C, 68.47;
3
2-(2-Oxoazocan-1-yl)propanal from 4: H NMR (400 MHz, CDCl ) d
H
12NO
3
1.34 (d, J = 7.5 Hz, 3H), 1.60–1.84 (m, 6H), 2.60–2.65 (m, 2H), 3.35–
H, 3.63; N, 4.20. Found: C, 68.44; H, 3.72; N, 4.24.
3.43 (m, 2H), 3.57 (t, J = 6.5 Hz, 2H), 4.44 (q, J = 7.5 Hz, 1H), 9.52
1
13
Ligand L5: H NMR (400 MHz, CDCl
3
) d 2.26 (s, 3H), 2.30 (s, 3H),
(s, 1H); C NMR (100 MHz, CDCl
37.6, 44.5, 62.5, 176.4, 199.1; Anal. Calcd for C10
3
) d 12.4, 23.7, 27.6, 29.7, 30.2,
17NO : C, 65.54;
2
7
1
.40 (s, 3H), 6.86–6.99 (m, 2H), 7.24–7.35 (m, 4H), 7.35–7.40 (m, 2H),
H
2
13
.53 (d, J = 7.4 Hz, 2H); C NMR (100 MHz, CDCl
22.6, 125.7, 126.4, 128.4, 129.5, 130.4, 131.6, 136.3, 149.4, 149.7;
) d 148.7; HRMS calcd for C21
M+H) : 351.1150. Found: 351.1143; Anal. Calcd for C21
3
) d 18.4, 20.4,
H, 9.35; N, 7.64. Found: C, 65.49; H, 9.28; N,7.62.
3
1
1
P
P
3
2-(9H-Carbazol-9-yl)propanal from 5: H NMR (400 MHz, CDCl ) d
NMR (162 MHz, CDCl
(
3
H
20
O
3
1.73 (d, J = 7.0 Hz, 3H), 5.18 (q, J = 7.0 Hz, 1H), 7.23–7.33 (m, 4H),
+
13
H O
19 3
P: C,
7.41–7.49 (m, 2H), 8.14 (d, J = 7.4 Hz, 2H), 9.94 (s, 1H); C NMR
7
1.99; H, 5.47. Found: C, 71.63; H, 5.53.
(100 MHz, CDCl
140.0, 200.7; Anal. Calcd for C15
Found: C, 80.60; H, 5.84; N, 6.30.
3
) d 12.9, 59.1, 109.1, 120.3, 121.1, 124.1, 126.5,
1
Ligand L6: H NMR (400 MHz, CDCl
.14 (s, 2H), 7.24–7.40 (m, 6H), 7.52 (d, J = 7.8 Hz, 2H); C NMR
100 MHz, CDCl ) d 14.1, 30.8, 34.6, 122.5, 125.5, 125.9, 127.8, 128.7,
3
) d 1.50 (s, 18H), 2.31 (s, 3H),
H
13NO: C, 80.69; H, 5.87; N, 6.27.
1
3
7
(
1
1
4
7
3
22. Lazzaroni, R.; Settambolo, R.; Uccello-Barretta, G. Organometallics
1995, 14, 4644.
23. Gleich, D.; Hutter, J. Chem. Eur. J. 2004, 10, 2435.
24. Alagona, G.; Ghio, C.; Lazzaroni, R.; Settambolo, R. Organometal-
lics 2001, 20, 5394.
3
1
29.5, 131.5, 136.2, 143.6, 151.9; P NMR (162 MHz, CDCl
48.0; HRMS calcd for C27
57.1925; Anal. Calcd for C27
4.38; H, 7.25.
3
) d
P (M+Na) : 457.1909. Found:
31 3
H O P: C, 74.63; H, 7.19. Found: C,
+
H
31NaO
3
2
1. General hydroformylation procedure: All hydroformylation reactions
were carried out in a 30 mL stainless-steel autoclave. An example is
given for N-vinylphthalimide 1. A glass liner containing a stirrer bar
25. Jongsma, T.; Challa, G.; Van Leeuwen, P. W. N. M. J. Organomet.
Chem. 1991, 421, 121.
26. Van Rooy, A.; Orij, E. N.; Kamer, P. C. J.; Van Leeuwen, P. W. N.
M. Organometallics 1995, 14, 34.
27. Botteghi, C.; Cazzolato, L.; Marchetti, M.; Paganelli, S. J. Org.
Chem. 1995, 60, 6612.
28. Kollar, L.; Heil, B.; Sandor, P. J. Organomet. Chem. 1989, 379, 191.
29. Knolker, H. J. Curr. Org. Synth. 2004, 1, 309.
was charged with 1 (0.6 mmol), the catalyst precursor Rh(acac)(CO)
2
À3
(3.87 Â 10 mmol) and a ligand (0.012 mmol) in toluene (3 mL).
Next, the vessel was sealed, and 20 bar of a mixture of hydrogen and
carbon monoxide (1:1) was introduced and the autoclave was then
placed in an oil bath preheated to 80 °C for a period of time given.