Increased Efficacies of an Individual Catalytic Site in Clustered Multivalent Dendritic Catalysts
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738, 696 cmÀ1
;
1H NMR (400 MHz, CDCl3): d=7.41–7.35
for C86H118Cl4N4O5P4Pd2 : C 58.48, H 6.73, N 3.17; found: C
57.80, H 6.78, N 3.18.
(m, 8H) 7.28–7.26 (m, 12H), 3.56 (d, J=2.5 Hz, 4H), 3.43–
3.36 (m, 16H), 3.28 (t, J=4.9 Hz, 2H), 3.21 (t, J=5.2 Hz,
2H) 2.91 (t, J=5.4 Hz, 2H), 2.47 (band, 12H), 1.70–1.53 (m,
20H), 1.31 (band, 12H), 0.89 (t, J=6.4 Hz, 9H); 13C NMR
(100 MHz, CDCl3): d=138.2, 138.1, 133.1, 133.0, 128.5,
128.4, 128.3, 71.0, 68.8, 50.7, 29.6, 28.4, 27.3, 22.5, 14.0;
31P NMR (162 MHz, CDCl3): d=À28.5; HR-MS: m/z=
1044.7251 [M+2O+H]+, calcd. for C62H100N3O5P2:
1044.7087.
10: A mixture of (CH2O)n (0.067 g, 2.23 mmol) and
Ph2PH (0.44 g, 2.34 mmol) in MeOH (4 mL) was heated at
708C for 10 min. and then cooled. To this reaction mixture,
a solution of the dendritic amine 9 (0.33 g, 0.53 mmol) in
MeOH (4 mL) was added and the reaction was followed fur-
ther as given in the general procedure I, to afford the bi-
sphosphinomethyl intermediate as a glassy liquid; yield:
0.73 g (97%). FT-IR (neat): n=3053, 2932, 2858, 2801, 1482,
To
a
solution of the above intermediate (0.115 g,
(COD)Cl2 (0.032 g,
1465, 1438, 1368, 1166, 1116, 741, 696 cmÀ1 1H NMR
;
0.112 mmol) in CH2Cl2 (5 mL), Pd
A
(400 MHz, CDCl3): d=7.40–7.37 (m, 16H) 7.27–7.25 (m,
24H), 3.55 (d, J=3.0 Hz, 8H), 3.42–3.35 (m, 12H), 3.27 (t,
J=6.3 Hz, 4H), 3.20 (t, J=6.5 Hz, 4H), 2.90 (t, J=6.9 Hz,
4H), 2.47–2.42 (m, 12H), 1.70–1.53 (m, 20H), 1.32–1.28 (m,
8H), 0.89 (t, J=6.7 Hz, 6H); 13C NMR (100 MHz, CDCl3):
d=138.2, 138.1, 133.2, 133.0, 128.4, 128.3,128.2, 71.0, 69.2,
69.0, 68.8, 58.8, 58.7, 58.6, 53.2, 50.9, 50.8, 29.5, 28.4, 27.4,
26.8, 22.5, 14.0; 31P NMR (162 MHz, CDCl3): d=À28.5; ES-
0.112 mmol) was added and the reaction was stirred for 2 h
at room temperature, solvent removed and the residue was
extracted with hexane, concentrated and dried to afford the
dendritic phosphine-Pd complex 6, as a brownish yellow
liquid; yield: 0.12 g (89%). FT-IR (neat): n=3073, 3055,
2974, 2927, 2856,1483, 1436, 1307, 1187, 1102, 873, 846, 740,
691, 560, 512 cmÀ1 1H NMR (400 MHz, CDCl3): d=7.82–
;
7.73 (m, 8H) 7.51–7.35 (m, 12H), 3.43–3.36 (m, 22H), 3.17
(t, J=6.5 Hz, 2H), 2.67 (b, 2H), 2.51 (band, 12H), 1.71
(band, 14H), 1.61–1.53 (m, 6H), 1.31 (band, 12H), 0.89 (t,
J=5.9 Hz, 9H); 13C NMR (100 MHz, CD2Cl2): d=134.3,
134.2, 131.9, 131.3, 131.2, 129.6, 129.0, 128.9, 71.5, 68.3, 68.0,
59.5, 57.2, 56.7, 50.9, 29.7, 28.7, 27.2, 22.9, 14.2; 31P NMR
(162 MHz, CD2Cl2): d=8.5; elemental analysis calcd. (%)
for C62H99Cl2N3O5P2Pd: C 61.7, H 8.28, N 3.49; found: C
60.9, H 8.25, N 3.51.
MS:
C86H119N4O5P4: 1411.8131.
To solution of the above intermediate (0.132 g,
0.093 mmol) in CH2Cl2 (5 mL), Pd(COD)Cl2 (0.053 g,
m/z=1411.8140
[M+O+H]+,
calcd.
for
a
AHCTUNGTRENNUNG
0.187 mmol) was added and the reaction was followed as
given in the general procedure II, to afford the dendritic
phosphine-Pd complex 10, as a yellow-orange solid; yield:
0.16 g (97%); mp 112–1158C; FT-IR (neat): n=3073, 3055,
2974, 2927, 2856, 1483, 1436, 1307, 1187, 1102, 873, 846, 740,
1
8: A mixture of (CH2O)n (0.116 g, 3.86 mmol) and Ph2PH
(0.75 g, 4.05 mmol) in MeOH (4 mL) was heated at 708C for
10 min and then cooled. To this reaction mixture, a solution
of the dendritic amine 7 (0.57 g, 0.92 mmol) in MeOH
(4 mL) was added and the reaction was followed further as
given in the general procedure I, to afford the bisphosphino-
methyl intermediate as a glassy liquid; 1.25 g (96%). FT-IR
(neat): n=3070, 3053, 2931, 2856, 2800, 1950, 1890, 1736,
691, 560, 512 cmÀ1; H NMR (300 MHz, CD2Cl2): d=7.78–
7.72 (m, 16H) 7.47–7.33 (m, 24H), 3.34–3.25 (m, 28H), 3.15
(t, J=5.7 Hz, 4H), 2.95 (t, J=5.7 Hz, 4H), 2.59 (t, J=
6.3 Hz, 12H), 1.74 (band, 8H), 1.44–1.42 (m, 8H), 1.23–1.18
(m, 8H), 0.80 (t, J=6.9 Hz, 6H); 13C NMR (75.5 MHz,
CD2Cl2): d=134.4, 134.3, 131.9, 129.7, 129.0, 128.9, 71.4,
69.1, 68.4, 68.2, 59.7, 59.5, 59.4, 57.3, 56.7, 51.0, 29.8, 28.8,
26.3, 22.9, 14.2; 31P NMR (162 MHz, CD2Cl2): d=8.4; ele-
mental analysis calcd. (%) for C86H118Cl4N4O5P4Pd2: C
58.48, H 6.73, N 3.17; found: C 57.80, H 6.78, N 3.18.
1586, 1481, 1434, 1158, 1114, 741, 696 cmÀ1
;
1H NMR
(400 MHz, CDCl3): d=7.41–7.37 (m, 16H) 7.27–7.26 (m,
24H), 3.55 (d, J=3.2 Hz, 8H), 3.41–3.34 (m, 12H), 3.27 (t,
J=6.4 Hz, 4H), 3.21 (t, J=6.6 Hz, 4H), 2.91 (t, J=6.8 Hz,
4H), 2.45 (band, 12H), 1.70–1.52 (m, 20H), 1.32–1.28 (m,
8H), 0.88 (t, J=6.7 Hz, 6H); 13C NMR (100 MHz, CDCl3):
d=138.2, 138.1, 133.2, 133.0, 128.4, 128.3, 128.2, 71.0, 69.1,
69.0, 68.8, 58.8, 58.7, 58.6, 53.2, 50.8, 50.7, 29.4, 28.4, 26.8,
22.5, 14.0; 31P NMR (162 MHz, CDCl3): d=À28.5; ES-MS:
m/z=1427.8180 [M+2O+H]+; calcd. for C86H119N4O6P4:
1427.8080.
12: A mixture of (CH2O)n (0.16 g, 5.2 mmol) and Ph2PH
(1.0 g, 5.42 mmol) in MeOH (4 mL) was heated at 708C for
10 min. and then cooled. To this reaction mixture, a solution
of the dendritic amine 11 (0.50 g, 0.82 mmol) in MeOH
(4 mL) was added and the reaction was followed further as
given in the general procedure I, to afford the bisphosphino-
methyl intermediate as a foamy solid; yield: 1.4 g (95%).
FT-IR (neat): n=3053, 2952, 2932, 2861, 2801, 1480, 1437,
1
1176, 1120, 741, 749, 696 cmÀ1; H NMR (400 MHz, CDCl3):
To a solution of the above intermediate (0.124 g, 87.9
mmol) in CH2Cl2 (5 mL), PdACTHNUGTRENNUG(COD)Cl2 (0.05 g, 0.176 mmol)
d=7.40–7.34 (m, 24H) 7.27–7.25 (m, 36H), 3.54 (band,
12H), 3.40–3.33 (m, 8H), 3.27–3.24 (m, 6H), 3.20–3.16 (m,
6H), 2.90 (t, J=6.6 Hz, 6H), 2.48 (band, 12H), 1.68–1.52
(m, 20H), 1.31–1.25 (m, 4H), 0.88 (t, J=6.8 Hz, 3H);
13C NMR (100 MHz, CDCl3): d=138.2, 138.1, 133.0, 128.5,
128.3, 128.2, 71.0, 68.8, 58.7, 50.8, 29.4, 28.3, 26.8, 22.5, 14.0;
31P NMR (162 MHz, CDCl3): d=À28.5; ES-MS: m/z=
1826.9000 [M+2O+H]+, calcd. for C110H138N5O7P6:
1826.9022.
was added and the reaction was followed as given in the
general procedure II, to afford the dendritic phosphine-Pd
complex 8, as a yellow-orange solid; yield: 0.15 g (94%); mp
85–878C; FT-IR (neat): n=3073, 3055, 2974, 2927,
2856,1483, 1436, 1307, 1187, 1102, 873, 846, 740, 691, 560,
512 cmÀ1 1H NMR (300 MHz, CD2Cl2): d=7.86–7.79 (m,
;
16H) 7.55–7.41 (m, 24H), 3.36–3.29 (m, 20H), 3.23 (t, J=
6.6 Hz, 4H), 3.03 (t, J=5.7 Hz, 4H), 2.68 (t, J=6.0 Hz, 4H),
2.38 (band, 12H), 1.66–1.47 (m, 20H), 1.29–1.26 (m, 8H),
0.87 (t, J=6.8 Hz, 6H); 13C NMR (75.5 MHz, CD2Cl2): d=
134.4, 134.3, 132.0, 129.0, 128.9, 71.3, 69.4, 69.2, 68.1, 59.7,
57.4, 56.8, 51.3, 29.9, 28.8, 26.4, 23.0, 14.2; 31P NMR
(162 MHz, CD2Cl2): d=8.4; elemental analysis calcd. (%)
To
a
solution of the above intermediate (0.15 g,
(COD)Cl2 (0.071 g,
0.083 mmol) in CH2Cl2 (5 mL), PdAHCNUTGTRENNUNG
0.25 mmol) was added and the reaction was followed as
given in the general procedure II, to afford the dendritic
phosphine-Pd complex 12, as a yellow solid; yield: 0.18 g
(94%); mp 187–1898C; FT-IR (neat): n=3073, 3055, 2974,
Adv. Synth. Catal. 2009, 351, 2379 – 2390
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2387