Asymmetric Allylic Substitution Reactions
FULL PAPER
124.2 (CH=), 124.3 (CH=), 124.4 (CH=), 124.6 (CH=), 125.5 (CH=),
126.2 (CH=), 126.4 (CH=), 126.5 (CH=), 126.6 (CH=), 126.9 (CH=),
127.2 (CH=), 127.5 (CH=), 127.6 (CH=), 127.8 (CH=), 128.2 (CH=),
128.4 (CH=), 129.3 (CH=), 132.8 (C), 133.1 (C), 133.3 (C), 133.4 (C),
136.8 (C), 138.1 (C), 138.5 (C), 139.9 (C), 140.5 (C), 145.9 (C), 146.2(C),
146.6 ppm (C); 31P NMR (CDCl3): d=143.9 (br), 151.2ppm (s); elemen-
tal analysis calcd (%) for C70H93NO5P2: C 77.10, H 8.60, N 1.28; found: C
77.12, H 8.61, N 1.31.
tBu), 1.52(m, 2H; CH 2), 3.21 (m, 1H; NH), 3.26 (m, 1H; CH-N), 3.62
(m, 1H; CH2-O), 3.82(m, 1H; CH 2-O), 7.10–7.50 ppm (m, 8H; CH=);
13C NMR (CDCl3): d=10.6 (CH3), 29.9 (CH2), 31.2(CH 3, tBu), 31.3
(CH3, tBu), 31.4 (CH3, tBu), 31.5 (CH3, tBu), 31.6 (CH3, tBu), 31.7 (CH3,
tBu), 31.8 (CH3, tBu), 31.9 (CH3, tBu), 34.8 (C, tBu), 35.5 (C, tBu), 53.1
(m; CH-N), 66.8 (m; CH-O), 124.1 (CH=), 124.3 (CH=), 124.4 (CH=),
126.2 (CH=), 126.7 (CH=), 126.8 (CH=), 132.9 (C), 133.1 (C), 133.2 (C),
139.9 (C), 140.2(C), 140.4 (C), 146.3 (C), 146.5 (C), 146.8 (C), 147.3 ppm
(C); 31P NMR (CDCl3): d=139.7 (s), 150.3 ppm (s); elemental analysis
calcd (%) for C60H89NO5P2: C 74.58, H 9.28, N 1.45; found: C 74.62, H
9.31, N 1.47.
1
3d: Yield: 0.34 g, 36%. H NMR (C6D6): d=0.25 (s, 9H; CH3-Si), 0.29 (s,
9H; CH3-Si), 0.37 (s, 9H; CH3-Si), 0.39 (s, 9H; CH3-Si), 3.79 (s, 1H; NH),
4.96 (m, 1H; CH-N), 5.71 (m, 1H; CH-O), 6.40–7.40 ppm (m, 22H; CH=);
13C NMR (C6D6): d=0.4 (CH3-Si), 0.6 (CH3-Si), 0.7 (CH3-Si), 61.6 (d,
3
7a: Yield: 0.51 g, 52%. 1H NMR (CDCl3): d=0.71 (d, JH-H =4.4 Hz, 3H;
J
C-P =12.8 Hz; CH-N), 83.1 (CH-O), 124.8 (CH=), 125.1 (CH=), 125.3
CH3), 0.79 (d, 3JH-H =4.4 Hz, 3H; CH3,), 1.36 (s, 18H; CH3, tBu), 1.37 (s,
18H; CH3, tBu), 1.45 (s, 9H; CH3, tBu), 1.48 (s, 27H; CH3, tBu), 1.80 (m,
1H; CH), 1.52(m, 2H; CH 2), 3.16 (m, 1H; NH), 3.32(m, 1H; CH-N),
3.66 (m, 1H; CH2-O), 3.79 (m, 1H; CH2-O), 7.10–7.50 ppm (m, 8H;
CH=); 13C NMR (CDCl3): d=18.1 (CH3), 18.7 (CH3), 30.4 (m; CH), 31.2
(CH3, tBu), 31.3 (CH3, tBu), 31.4 (CH3, tBu), 31.5 (CH3, tBu), 31.7 (CH3,
tBu), 31.8 (CH3, tBu), 34.8 (C, tBu), 34.9 (C), 35.6 (C, tBu), 57.2(m; CH-
N), 66.1 (m; CH-O), 124.1 (CH=), 124.3 (CH=), 124.4 (CH=), 126.4
(CH=), 126.6 (CH=), 126.7 (CH=), 132.9 (C), 133.1 (C), 133.3 (C), 140.0
(C), 140.3 (C), 145.8 (C), 145.9 (C), 146.4 (C), 147.1 ppm (C); 31P NMR
(CDCl3): d=138.8 (s), 150.0 ppm (s); elemental analysis calcd (%) for
C61H91NO5P2: C 74.74, H 9.36, N 1.43; found: C 74.86, H 9.42, N 1.42.
(CH=), 125.7 (CH=), 126.0 (C), 127.9 (CH=), 128.1 (CH=), 128.4 (CH=),
128.8 (CH=), 131.5 (C), 132.1 (C), 132.5 (CH=), 132.7 (CH=), 133.0
(CH=), 133.4 (CH=), 135.4 (CH=), 135.6 (CH=), 135.8 (CH=), 135.9
(CH=), 137.2(C), 138.2(C), 138.8 (C), 155.3 (C), 155.5 (C), 156.3 (C),
156.7 ppm (C); 31P NMR (C6D6): d=146.9 (br), 153.5 ppm (s); elemental
analysis calcd (%) for C50H61NO5P2Si4: C 64.55, H 6.61, N 1.51; found: C
64.57, H 6.70, N 1.58.
1
3 f: Yield: 0.22 g, 20%. H NMR (C6D6): d=0.11 (s, 9H; CH3-Si), 0.12(s,
9H; CH3-Si), 0.79 (s, 9H; CH3-Si), 0.92(s, 9H; CH -Si), 3.45 (s, 1H; NH),
3
4.76 (m, 1H; CH-N), 5.34 (m, 1H; CH-O), 6.40–8.40 ppm (m, 30H; CH=);
13C NMR (C6D6): d=0.2(CH 3-Si), 0.6 (CH3-Si), 0.9 (CH3-Si), 61.8 (d,
J
C-P =22.4 Hz; CH-N), 84.2 (CH-O), 124.1 (CH=), 124.3 (CH=), 125.2
8a: Yield: 0.42g, 42%. 1H NMR (CDCl3): d=0.90 (s, 9H; CH3), 1.56 (s,
18H; CH3, tBu), 1.57 (s, 18H; CH3, tBu), 1.68 (s, 9H; CH3, tBu), 1.69 (s,
18H; CH3, tBu), 1.71 (s, 9H; CH3, tBu), 3.36 (m, 1H; NH), 3.46 (m, 1H;
CH-N), 3.79 (m, 1H; CH2-O), 4.09 (m, 1H; CH2-O), 7.30–7.70 ppm (m,
8H; CH=); 13C NMR (CDCl3): d=27.2 (CH3), 31.4 (CH3, tBu), 31.6
(CH3, tBu), 31.8 (CH3, tBu), 31.9 (CH3, tBu), 34.8 (C, tBu), 35.0 (C, tBu),
35.8 (C, tBu), 62.3 (m; CH-N), 66.4 (m; CH-O), 124.2 (CH=), 124.4
(CH=), 124.6 (CH=), 126.8 (CH=), 126.9 (CH=), 133.1 (C), 133.2(C),
133.5 (C), 140.1 (C), 140.4 (C), 140.7 (C), 146.0 (C), 146.4 (C), 146.7 (C),
147.0 ppm (C); 31P NMR (CDCl3): d=165.0 (s), 176.5 ppm (s); elemental
analysis calcd (%) for C62H92NO5P2: C 74.89, H 9.43, N 1.41; found: C
74.94, H 9.52, N 1.49.
9a: Yield: 0.62g, 63%. 1H NMR (C6D6): d=1.25 (s, 9H; CH3, tBu), 1.29
(s, 18H; CH3, tBu), 1.30 (s, 9H; CH3, tBu), 1.45 (s, 9H; CH3, tBu), 1.49
(s, 9H; CH3, tBu), 1.53 (s, 9H; CH3, tBu), 1.56 (s, 9H; CH3, tBu), 3.23
(m, 3H; NH, CH2-N), 5.32(m, 1H; CH-O), 6.90–7.60 ppm (m, 13H;
CH=); 13C NMR (C6D6): d=31.7 (CH3, tBu), 31.9 (CH3, tBu), 32.0 (CH3,
tBu), 35.0 (C, tBu), 35.9 (C, tBu), 47.9 (m; CH-N), 79.5 (m; CH-O), 124.4
(CH=), 124.7 (CH=), 124.9 (CH=), 126.0 (CH=), 126.9 (CH=), 127.1
(CH=), 127.4 (CH=), 127.7 (CH=), 128.8 (CH=), 128.9 (CH=), 129.6
(CH=), 133.8 (C), 134.2(C), 134.4 (C), 140.0 (C), 140.8 (C), 140.9 (C),
141.0 (C), 141.2(C), 146.5 (C), 146.6 (C), 146.9 (C), 147.3 ppm (C);
31P NMR (C6D6): d=145.9 (s), 147.7 ppm (s); elemental analysis calcd
(%) for C64H89NO5P2: C 75.78, H 8.84, N 1.38; found: C 75.81, H 8.87, N
1.43.
(CH=), 125.4 (CH=), 125.9 (CH=), 127.0 (C), 127.1 (CH=), 127.2 (C),
127.5 (CH=), 127.6 (CH=), 127.7 (CH=), 128.5 (CH=), 128.7 (CH=),
129.0 (CH=), 129.2 (CH=), 129.3 (CH=), 130.4 (C), 131.1 (CH=), 131.6
(CH=), 131.9 (CH=), 132.3 (CH=), 133.5 (CH=), 133.6 (CH=), 134.3
(CH=), 134.7 (C), 134.8 (CH=), 135.3 (CH=), 136.2(CH =), 137.8 (C),
138.3 (CH=), 139.2(CH =), 139.3 (C), 139.5 (C), 152.9 (C), 153.4 (C),
154.3 (C), 154.7 ppm (C); 31P NMR (C6D6): d=136.9 (s), 159.2ppm (s);
elemental analysis calcd (%) for C66H69NO5P2Si4: C 70.12, H 6.15, N
1.24; found: C 70.22, H 6.12, N 1.26.
4a: Yield: 0.2g, 20%. 1H NMR (C6D6): d=1.20 (s, 9H; CH3, tBu), 1.23
(m, 3H; CH3), 1.24 (s, 18H; CH3, tBu), 1.25 (s, 9H; CH3, tBu), 1.40 (br,
9H; CH3, tBu), 1.46 (br, 9H; CH3, tBu), 1.53 (br, 9H; CH3, tBu), 1.63
(br, 9H; CH3, tBu), 2.26 (br, 1H; CH3-N), 4.27 (br, 1H; CH-N), 5.44 (br,
1H; CH-O), 6.95–7.6 ppm (m, 13H; CH=); 13C NMR (C7D8): d=31.3
(CH3, tBu), 31.4 (CH3, tBu), 31.6 (CH3, tBu), 31.9 (CH3, tBu), 34.6 (C,
tBu), 35.5 (C, tBu), 35.6 (C, tBu), 36.5 (CH3-N), 53.2(br, CH-N), 82.0
(br, CH-O), 124.1 (CH=), 124.4 (CH=), 124.9 (CH=), 125.1 (CH=), 125.3
(CH=), 125.6 (CH=), 126.6 (CH=), 126.7 (CH=), 126.9 (CH=), 127.9
(CH=), 128.4 (CH=), 128.5 (CH=), 128.6 (CH=), 128.8 (CH=), 129.0
(CH=), 129.3 (CH=), 133.2(C), 133.9 (C), 137.4 (C), 138.8 (C), 140.2(C),
140.6 (C), 140.8 (C), 146.0 (C), 146.3 (C), 146.4 (C), 146.9 ppm (C);
31P NMR (C6D6): d=145.1 (br), 148.2ppm (s); elemental analysis calcd
(%) for C66H93NO5P2: C 76.05, H 8.99, N 1.34; found: C 76.11, H 9.02, N
1.37.
5a: Yield: 0.63 g, 62%. 1H NMR (CDCl3): d=1.27 (s, 9H; CH3, tBu),
1.35 (s, 9H; CH3, tBu), 1.36 (s, 9H; CH3, tBu), 1.37 (s, 9H; CH3, tBu),
1.38 (s, 9H; CH3, tBu), 1.41 (s, 9H; CH3, tBu), 1.42(s, 9H; CH 3, tBu),
1.43 (s, 9H; CH3, tBu), 3.68 (m, 1H; NH), 3.80 (m, 1H; CH2-O), 3.87 (m,
1H; CH2-O), 4.36 (m, 1H; CH-N), 6.90–7.50 ppm (m, 13H; CH=);
10 f: Yield: 0.57 g, 59%. 31P NMR (C6D6): d=133.8 (s), 146.9 ppm (s);
1H NMR (C6D6): d=0.41 (s, 9H; CH3-Si), 0.49 (s, 9H; CH3-Si), 0.51 (s,
9H; CH3-Si), 0.55 (s, 9H; CH3-Si), 2.50 (m, 1H; CH2-N), 2.67 (m, 1H;
CH2-N), 2.97 (m, 1H; NH), 3.11 (m, 1H; CH-O),3.57 (m, 1H; CH-O),
6.80–8.10 ppm (m, 20H; CH=); 13C NMR (C6D6): d=0.4 (CH3-Si), 0.6
(CH3-Si), 0.7 (CH3-Si), 41.4 (m; CH2-N), 66.1 (m; CH2-O), 125.1 (CH=),
125.4 (CH=), 126.0 (C), 127.1 (CH=), 127.2 (CH=), 127.4 (CH=), 128.8
(CH=), 128.9 (CH=), 129.0 (CH=), 129.1 (CH=), 129.2 (CH=), 129.4 (C),
129.6 (CH=), 131.2(CH =), 131.4 (CH=), 131.8 (CH=), 132.0 (CH=),
132.4 (CH=), 133.0 (CH=), 134.7 (C), 135.0 (CH=), 135.1 (CH=), 137.5
(CH=), 137.7 (CH=), 137.8 (CH=), 138.0 (CH=), 144.8 (C), 145.3 (C),
152.6 (C), 153.5 (C), 153.6 (C), 154.4 ppm (C); elemental analysis calcd
(%) for C54H61NO5P2Si4: C 66.29, H 6.28, N 1.43; found: C 66.34, H 6.32,
N 1.48.
13C NMR (CDCl3): d=31.1 (CH3, tBu), 31.2(CH , tBu), 31.3 (CH3, tBu),
3
31.5 (CH3, tBu), 31.6 (CH3, tBu), 31.7 (CH3, tBu), 31.8 (CH3, tBu), 31.9
(CH3, tBu), 35.4 (C, tBu), 35.4 (C, tBu), 35.5 (C, tBu), 35.6 (C, tBu), 56.0
(m; CH-N), 68.8 (m; CH-O), 124.1 (CH=), 124.3 (CH=), 124.4 (CH=),
124.5 (CH=), 126.2 (CH=), 126.6 (CH=), 126.7 (CH=), 127.5 (CH=),
127.6 (CH=), 128.4 (CH=), 128.5 (CH=), 129.3 (CH=), 132.8 (C), 133.1
(C), 133.7 (C), 138.1 (C), 139.9 (C), 140.2(C), 140.4 (C), 141.1 (C), 145.8
(C), 146.1 (C), 146.3 (C), 146.4 (C), 146.6 (C), 146.9 (C), 147.1 ppm (C);
31P NMR (CDCl3): d=137.7 (s), 148.6 ppm (s); elemental analysis calcd
(%) for C64H89NO5P2: C 75.78, H 8.84, N 1.38; found: C 76.01, H 8.91, N
1.37.
General procedure for the preparation of [PdACHTREUNG
plexes: The corresponding ligand (0.05 mmol) and the complex [PdACHTREUNG
1
3
6a: Yield: 0.57 g, 59%. H NMR (CDCl3): d=0.66 (t, JH-H =7.6 Hz, 3H;
CH3), 1.35 (s, 9H; CH3, tBu), 1.36 (s, 9H; CH3, tBu), 1.37 (s, 18H; CH3,
tBu), 1.46 (s, 9H; CH3, tBu), 1.47 (s, 9H; CH3, tBu), 1.48 (s, 18H; CH3,
Cl)(h3-1,3-allyl)]2 (0.025 mmol) were dissolved in CD2Cl2 (1.5 mL) at
room temperature under argon. AgBF4 (9.8 mg, 0.5 mmol) was added
after 30 min and the mixture was stirred for 30 min. The mixture was
Chem. Eur. J. 2008, 14, 944 – 960
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