Article
Organometallics, Vol. 29, No. 7, 2010 1837
isotopic effect (k /k ≈ 1) indicates thet the O-H(D) bond
(m, 1H), 3.42 (m, 2H), 3.20 (s, 3H), 2.78-2.63 (m, 2H), 1.97 (s,
3H), 1.95 (s, 3H), 1.77 (s, 3H), 1.51 (d, J=6.8 Hz, 3H), 1.16 (s,
D
H
activation proceeds rapidly.
1
3
1
3
1
9
H). C{ H} NMR (CDCl , 125 MHz): δ 208.2, 179.5, 142.2,
Further studies in order to determine the asymmetric
catalytic behavior of the enantiomerically pure metal com-
plexes are underway.
3
36.4, 129.0, 128.9, 128.5, 127.6, 126.2, 121.7, 120.6, 103.4, 99.8,
6.5, 89.0, 80.4, 66.7, 66.2, 38.5, 28.3, 26.4, 10.2, 9.7, 9.6, 8.9.
þ
HRMS (ESI-TOF): m/z [M] calcd for C30
5
H
36
-
N
3
ORu,
1
56.1910; found, 556.1910. IR (KBr): ν(CO) 1919 cm .
1
Experimental Section
3
5B (6 mg, 0.0085 mmol, 16%): H NMR (500 MHz, CDCl ):
δ 7.60 (d, J=7.2 Hz, 2H), 7.44-7.36 (m, 5H), 7.30 (t, J=7.5 Hz,
2H), 7.20 (d, J=7 Hz, 1H), 6.73 (br, 1H), 6.33 (s, 1H), 5.13 (dd,
J=12.2 Hz J=2.2 Hz, 1H), 3.74 (br, 2H), 3.63 (s, 3H), 2.76-2.64
(m, 3H), 1.81 (s, 3H), 1.72 (s, 3H), 1.46 (d, J=6.5 Hz, 3H), 1.41
7
9
General Procedures. Ligands 1 and 2 were synthesized
according to literature procedures. All other reagents were used
as received from commercial suppliers and used without further
purification. NMR spectra were recorded on a Varian Innova
1
3
1
3
(s, 3H), 1.16 (s, 3H). C{ H} NMR (CDCl , 125 MHz): δ 209.7,
3
00 and 500 MHz, using CDCl as solvent. Electrospray mass
3
180.3, 143.3, 136.8, 129.7, 129.5, 129.3, 129.2, 128.2, 127.1,
122.7, 121.3, 104.5, 99.9, 96.6, 90.4, 81.4, 67.7, 62.7, 39.5, 28.7,
24.2, 10.7, 10.3, 9.6, 9.2. HRMS (ESI-TOF): m/z [M] calcd for
spectra (ESI-MS) were recorded on a Micromass Quatro LC
instrument; nitrogen was employed as drying and nebulizing
gas. A QTOF I (quadrupole-hexapole-TOF) mass spectrometer
with an orthogonal Z-spray-electrospray interface (Micromass,
Manchester, UK) was used for high-resolution mass spectro-
metry (HRMS). The drying gas as well as nebulizing gas was
nitrogen at a flow of 400 L/h and 80 L/h, respectively.
Synthesis of 3. A solution of 1 (300 mg, 0.69 mmol) and
triruthenium dodecarbonyl (147 mg, 0.23 mmol) is refluxed in
toluene (10 mL) overnight. The resulting red solution with black
precipitate is evaporated to dryness and purified by column
chromatography (dichloromethane/acetone), yielding the
þ
C H N ORu, 556.1910; found, 556.1904. IR (KBr): ν(CO)
30 36 3
-
1
.
1918 cm
Synthesis of 6A and 6B. A solution of 4 (35 mg, 0.037 mmol)
and AgOTf (12 mg, 0.045 mmol) in 5 mL of dichloroethane was
stirred at room temperature for 10 min. Then (S)-(-)-R-methyl-
benzylamine (6 μL, 0.045 mmol) was added, the reaction
mixture was heated at 70 °C for 1 h, the yellow solution was
filtered through Celite, and the volatiles were removed under
vacuum. The crude was applied in a preparative TLC and eluted
several times with diethyl ether. Both diastereoisomers were
characterized:
1
ruthenium complex 3 (220 mg, 0.39 mmol, 57%). H NMR
(
1
300 MHz, CDCl ): δ 7.46 (m, 5H), 6.68 (d, J=2.1 Hz, 1H), 6.25
6A (5 mg, 0.0046 mmol, 12.5%): H NMR (500 MHz,
3
(
d, J=2.1 Hz, 1H), 5.15 (dd, J=2.7 Hz J=11.4 Hz, 1H), 3.75 (s,
CDCl ): δ 8.07 (d, J = 7 Hz, 1H), 7.42 (t, J = 7.5 Hz, 3H),
3
3
3
1
2
H), 2,76 (m, 2H), 2.29 (s, 3H), 2.02 (s, 3H), 1.96 (s, 3H), 1.47 (s,
H). C{ H} NMR (CDCl , 125 MHz): δ 209.1, 184.1, 137.8,
3
7.31-6.92 (m, 23H), 6.67 (d, J=8 Hz, 1H), 6.63 (br, 2H), 6.42 (d,
J=7.5 Hz, 2H), 6.32 (m, 3H), 6.26 (t, J=7.5 Hz, 1H), 6.16 (d, J=
11 Hz, 1H), 6.10 (br, 2H), 6.03 (br, 1H), 4.32 (d, J=18 Hz, 1H),
4.29 (t, J=6.5 Hz, 1H), 4.20 (d, J=16.5 Hz, 1H), 4.05 (d, J=11
Hz, 1H), 3.53 (d, J=16.5 Hz, 1H), 4.45 (d, J=14.5 Hz, 1H), 4.41
(d, J=18.5 Hz, 1H), 3.04 (s, 3H), 1.99 (d, J=15.5 Hz, 1H), 1.14
13
1
29.4, 129.0, 121.6, 119.6, 104.4, 99.1, 95.1, 89.8, 83.2, 67.7, 39.8,
9.1, 11.9, 11.1, 10.97, 10.52. MS (ESI): m/z [M - I] calcd for
þ
þ
C
C H N NaORu, 585.0; found, 484.9. HRMS (ESI-TOF):
m/z [M] calcd for C H N ORu, 435.1017; found, 435.1017.
2
22
H
25
N
2
ORu, 435.1; found, 435.0, [M þ Na] calcd for
2
2
25
2
þ
13
1
2
25
-
2
3
(d, 6.5 Hz, 3H). C{ H} NMR (CDCl , 125 MHz): δ 209.7,
1
IR (KBr): ν(CO) 1910 cm
.
1
1
6
80.2, 142.3, 142.1, 138.5, 138.4, 136.4, 136.0, 135.3, 132.9,
30.0-125.3, 122.5, 121.3, 113.0, 102.3, 100.5, 95.7, 87.1, 70.0,
2.3, 44.4, 39.2, 32.0, 31.7, 30.11, 29.8, 29.7, 28.4. MS (ESI-
Synthesis of 4. A solution of 2 (158 mg, 0.19 mmol) and
triruthenium dodecarbonyl (41 mg, 0.06 mmol) is refluxed in
toluene (10 mL) overnight. The resulting red solution with black
precipitate is evaporated to dryness and purified by column
chromatography (dichloromethane/acetone), yielding the
þ
TOF): m/z [M] calcd for C60
H
56
N
3
ORu, 936.3484; found,
-
1
9
36.3507. IR (KBr): ν(CO) 1925 cm . 1
B (5 mg, 0.0046 mmol, 12.5%): H NMR (500 MHz,
CDCl ): δ 7.91 (d, J = 8 Hz, 1H), 7.39-7.25 (m, 5H),
.19-7.13 (m, 8H), 7.10-6.97 (m, 8H), 7.0-6.77 (m, 6H), 6.58
br, 2H), 6.51 (d, J=8 Hz, 2H), 6.38 (t, J=7.5 Hz, 2H), 6.31 (t,
J=6.5 Hz, 1H), 6.25-6.20 (m, 3H), 4.29 (d, J=14.5 Hz, 1H),
.25 (d, J=11.5 Hz, 1H), 4.13 (d, J=16.5 Hz, 1H), 3.80 (m, 1H),
6
1
ruthenium complex 4 (100 mg, 0.11 mmol, 55%). H NMR
3
(
(
(
3
300 MHz, CDCl ): δ 7.17-6.30 (m, 30H), 6.63 (m, 1H), 5.94
m, 1H), 5.90 (d, J=11.1 Hz, 1H), 4.39 (d, J=17.4 Hz, 1H), 4.36
d, J=11.1 Hz, 1H), 4.08 (d, J=17.1 Hz, 1H), 3.56 (d, J=15.9
7
(
Hz, 1H), 3.40 (d, J=16.8 Hz, 1H), 3.34 (d, J=17.7 Hz, 1H), 3.17
d, J=16.8 Hz, 1H), 3.11 (d, J=15.9 Hz, 1H), 2.86 (d, J=16.2
4
(
Hz, 1H). C{ H} NMR (CDCl
3.75 (s, 3H), 3.58 (d, J=16.5 Hz, 1H), 3.35-3.20 (m, 3H), 3.08
(d, J=14.5 Hz, 1H), 3.39 (d, J=16 Hz, 1H), 2.39 (d, J=16.5 Hz,
1H), 0.94 (d, J=6.5 Hz, 1H). C{ H} NMR (CDCl , 125 MHz):
13
1
3
, 125 MHz): δ 208.0, 182.2,
1
3
1
140.0, 139.7, 139.2, 138.9, 138.2, 137.0, 130.6, 129.6,
129.0-127.4, 126.4-126.2, 125.7, 125.3, 121.7, 121.3, 107.5,
102.5, 99.2, 96.2, 89.1, 70.6, 44.4, 40.2, 34.4, 31.9, 31.5, 31.25.
3
δ 209.6, 181.2, 144.1, 141.4, 138.8, 138.5, 136.6, 136.0, 133.0,
130-126.9, 122.75, 112.5, 101.4, 96.2, 87.0, 71.1 63.8, 44.8, 40.0,
32.2, 30.3, 22.3. HRMS (ESI-TOF): m/z [M] calcd for
þ
þ
MS (ESI): m/z [M - I] calcd for C H N ORu, 815.26; found,
5
2
45
2
þ
8
15.2; [M - I þ CH CN] calcd for C H N ORu, 856.28;
C H N ORu, 936.3484; found, 936.3518. IR (KBr): ν(CO)
3
54 48
3
60 56
3
þ
-1
found, 856.2; [M þ Na] calcd for C H IN NaORu, 865.15;
1924 cm .
5
2
45
2
þ
found, 965.1. HRMS (ESI-TOF): m/z [M] calcd for
ORu, 815.2590; found, 815.2590. IR (KBr): ν(CO)
Catalytic Experiments. In THF. A solution of catalyst
(1 mol %) in 0.5 mL of THF is treated with AgOTf (1-2 mol %)
and stirred at room temperature for 10 min. Then 0.8 mmol
of substrate is added and the reaction heated to 55 °C followed by
52 45 2
C H N
-
1
1
923 cm
.
Synthesis of 5A and 5B. A solution of 3 (30 mg, 0.053 mmol)
1
and AgOTf (17 mg, 0.064 mmol) in 5 mL of dichloroethane was
stirred at room temperature for 10 min. Then (S)-(-)-R-methyl-
benzylamine (8 μL, 0.064 mmol) was added, the reaction
mixture was heated at 70 °C for 20 min, the yellow solution
was filtered through Celite, and the volatiles were removed
under vacuum. The crude was applied in a preparative TLC
and eluted several times with diethyl ether/hexane (8:2). Both
H NMR.
2 2
In H O. A solution of catalyst (0.2 mol %) in 4 mL of H O is
treated with AgOTf (0.2 mol %) and stirred at room tempera-
ture for 10 min. Then 0.4 mmol of substrate is added and the
1
reaction heated to 75 °C followed by H NMR.
Kinetic Isotopic Effect. A solution of 1 (0.9 mg, 0.2 mol %) in
2 2
4 mL of H O/D O is treated with AgOTf (0.3 mg, 0.2 mol %)
diastereoisomers were characterized:
5
and stirred at room temperature for 10 min. Then 3-buten-1-ol
(43 μL, 0.4 mmol) is added and the reaction heated to 75 °C.
1
A (6 mg, 0.0085 mmol, 16%): H NMR (500 MHz, CDCl ):
3
1
O, and the H
δ 7.60 (d, J=7 Hz, 2H), 7.44-7.36 (m, 3H), 7.24-7.18 (m, 5H),
.52 (s, 1H), 6.26 (s, 1H), 5.21 (dd, J=12.5 Hz J=2 Hz, 1H), 3.62
Aliquots (50 μL) are taken and dissolved in D
NMR spectra recorded.
2
6