T. Hammerer et al. / Tetrahedron: Asymmetry 23 (2012) 53–59
57
CP = 7.3 Hz, C) ppm; 31P{ H} NMR (CDCl
1
): d = 153.8 ppm; HRMS
4
.2. Preparation of ligands L1–L4
J
(
3
2
0
EI, 80 eV): calculated: 522.28111; found: 522.28181; ½
aꢁ
¼ þ
D
0
4
1
.2.1. (R
a
)-2,2 -Bis((2R,5R)-2,5-dimethylphospholan-1-yloxy)-
2 2
121:3 (c 1.033, CH Cl ).
0
,1 -binaphthyl L1
A
solution of (2R,5R)-1-chloro-2,5-dimethylphospholane
0
4
5
.2.4. (S
a
)-2,2 -Bis((2R,5R)-2,5-dimethylphospholan-1-yloxy)-
(
3
295 mg, 1.96 mmol), in toluene (3 ml) was added at ꢀ20 °C over
0
0
0
0
0
,5 ,6,6 ,7,7 ,8,8 -octahydro-1,1 -binaphthyl L4
The title compound was obtained by the procedure described
above using (S )-5,5 ,6,6 ,7,7 ,8,8 -octahydro-1,1 -binaphthyl-2,2 -
a
diol (376 mg, 1.27 mmol) as the diol. The product was obtained
after filtration over basic alumina as colourless solid.
0
0 min through a syringe pump to a mixture of (R)-1,1 -binaph-
0
thyl-2,2 -diol (280.4 mg, 0.98 mmol) and triethylamine (300
.16 mmol) in toluene (10 mL). The reaction mixture was stirred
lL,
0
0
0
0
0
0
2
at ꢀ20 °C for 1 h and then at ambient temperature overnight.
The reaction mixture was filtered through a PTFE membrane to re-
move the ammonium salt formed as a by-product. After evapora-
tion of the solvent,
recrystallised from hot acetonitrile. (385.9 mg, 75%); H NMR
CDCl ): d = 0.53–0.80 (m, 2H, CH ); 0.67 (d, 6H, HH = 7.7,
PH = 19.2; CH ); 0.86 (d, 6H, JHH = 6.9, JPH = 11.4; CH ); 0.89–1.01
m, 2H, CH); 1.15–1.35 (m, 2H, CH); 1.35–1.59 (m, 2H, CH);
a
(
449.5 mg; 86%).
1
H NMR (CDCl
3
): d = 0.93 (dd, JHH = 7.00 Hz, JHP = 18.33 Hz, 6H,
); 1.21–1.34
, CH); 1.81–1.92 (m, 2H,
); 2.22–2.33 (m, 2H, CH ); 2.60–2.70
2
) 6.87 (d, JHH = 8.31 Hz, 2H, Ar-H); 6.96 (d, JHH = 8.20 Hz,
a
white solid formed, which was
CH
m, 3H, CH
CH ); 1.98–2.11 (m, 2H, CH
m, 4H, CH
3
); 0.98 (dd, JHH = 7.71 Hz, JHP = 26.61 Hz, 6H, CH
3
1
(
2
, CH); 1.51–1.79 (m, 15H, CH
2
(
J
(
7
2
3
2
J
2
2
2
3
3
(
2
1
13
H, Ar-H) ppm; C NMR (CDCl
7.7 (s, CH ); 23.4 (d, JCP = 3.4 Hz, CH
); 35.2 (d, JCP = 2.8 Hz, CH ); 35.5 (d, JCP = 2.8 Hz, CH
CP = 12.6 Hz, CH); 42.3 (d, CP = 20.3 Hz, CH); 114.4 (d,
CP = 15.9 Hz, C); 128.5 (s, C); 129.4 (s, C); 130.4 (s, C); 130.5 (s,
3
): d = 12.9 (s, CH
3
); 17.4 (s, CH
); 29.6 (s,
); 40.5
3
);
.07–7.11 (m, 2H, Ar-H); 7.11–7.14 (m, 2H, Ar-H); 7.35–7.49 (m,
2
2
); 27.5 (s, CH
2
13
H, CH); 7.69–7.82 (m, 4H, Ar-H) ppm;
, JCP = 3.03 Hz), 17.19 (d, CH
, JCP = 3.36 Hz), 35.24 (d, CH , JCP = 3.17 Hz), 40.16
d, CH, JCP = 13.2 Hz), 42.41 (d, CH, JCP = 19.2 Hz), 119.96 (d, CH,
CP = 15.4 Hz), 122.19 (d, C, 3
CP = 2.07 Hz), 123.73 (s, CH), 125.81
s, CH), 126.12 (s, CH), 127.88 (s, CH), 129.09 (s, CH), 129.64 (s,
C
NMR (CDCl
3
):
CH
d,
2
2
2
d = 12.91 (d, CH
4.92 (d, CH
3
3
, JCP = 31.5 Hz),
(
J
J
3
(
J
(
2
2
J
31
1
3
C); 136.8 (s, C) ppm; P{ H} NMR (CDCl ): d = 155.6 ppm; HRMS
EI, 80 eV): calculated: 522.28111; found: 522.28142;
J
(
20
D
½
a
ꢁ
¼ þ36:9 (c 1.065, CH
2 2
Cl ).
CH), 134.25 (s, C), 153.36 (d, C, JCP = 6.6 Hz) ppm; 31P{ H} NMR
1
(
5
CDCl
15.3 [M ]; ½
3
): d = 159.4 ppm; MS (CI, 80 eV): calculated: 514.6; found:
+
20
D
4.3. Preparation of rhodium complexes
aꢁ
¼ þ186:8 (c 0.732, CH
2 2
Cl ).
0
4.3.1. [Rh(cycloocta-1,5-diene)L1]BF
At first, HBF O (0.120 mmol, 51 lL) was added to a solution
of (acetylacetonato)-(1,5-cyclooctadiene)-rhodium (I) (37.6 mg,
4
4
1
.2.2. (S
a
)-2,2 -Bis((2R,5R)-2,5-dimethylphospholan-1-yloxy)-
0
4
ꢂEt
2
,1 -binaphthyl L2
The title compound was obtained by the procedure described
above using (S)-1,1 -binaphthyl-2,2 -diol as the diol. The product
is a white solid, which was recrystallised from hot acetonitrile
0
0
0.120 mmol) in dry THF (3 mL). The solution was stirred for
1
0 min at ambient temperature, then a solution of L1 (63.3 mg,
1
0.120 mmol) in THF (3 mL) was added dropwise. During the addi-
tion, the colour of the solution turned from yellow to orange. After
stirring for 60 min, the solvent was removed under reduced pres-
(
J
J
1
2
(
(
CH
J
447.7 mg; 74%); H NMR (CDCl
3
): d = 0.59 (dd, JHH = 7.07 Hz,
); 0.82–1.03 (m, 5H, CH, CH ); 0.93 (dd,
HH = 7.40 Hz, JPH = 19.11 Hz, 6H, CH ); 1.50–1.60 (m, 2H, CH );
.63–1.74 (m, 5H, CH); 7.14–7.16 (m, 2H, Ar-H); 7.21–7.26 (m,
H, Ar-H); 7.43 (dd, 2H, JHH = 1.96 Hz, JPH = 8.89 Hz, CH); 7.78
PH = 11.45 Hz, 6H, CH
3
2
3
.
sure. The orange residue was dissolved in CH
resulting solution added dropwise to Et O (25 mL), whereupon a
yellow precipitate was formed. The mother liquor was removed
and the remaining yellow solid was washed with Et
O (3 ꢃ 5 mL)
and dried under reduced pressure (79.0 mg; 81%); H NMR
2 2
Cl (1 mL) and the
2
3
13
dd, 4H,
CDCl ): d = 12.9 (s, C
CP = 2.7 Hz); 35.5 (d, CH
CP = 14.5 Hz); 42.7 (d, CH, JCP = 20.0 Hz); 119.4 (d, JCP = 15.6 Hz,
CH); 122.9 (s, C); 124.2 (s, CH); 126.4 (s, CH); 126.7 (s, CH);
29.6 (s, CH); 130.3 (s, CH); 134.8 (s, CH); 134.3 (s, C); 153.8
J
HH = 8.5 Hz,
); 17.5 (s, Caliph.); 17.8 (s, C); 35.1 (d,
CP = 2.7 Hz); 41.0 (d, CH,
JPH = 21.23 Hz, Ar-H) ppm;
C NMR
2
3
.
1
2
,
J
2
, J
(
CD
2
Cl
2
): d = 0.02 (dd, JHH = 6.70 Hz, JHP = 13.16 Hz, 6H, CH
3
); 1.46
(
dd, JHH = 7.45 Hz, JPH = 16.93 Hz, 9H, CH
3
, CH); 1.58–1.79 (m, 4H,
CH); 1.93–2.07 (m, 2H, CH); 2.19–2.42 (m, 8H, CH); 2.42–2.53
(m, 2H, CH); 2.82–2.96 (m, 2H, CH); 5.12–5.26 (m, 4H, CH);
7.104 (d, JHH = 8.43 Hz, 2H, Ar-H); 7.31 (t, JHH = 7.69 Hz, 2H, Ar-
H); 7.42 (d, JHH = 8.89 Hz, 2H, Ar-H); 7.55 (t, 2H, JHH = 7.55 Hz, Ar-
H); 7.98 (d, JHH = 8.05 Hz, 2H, Ar-H); 8.10 (d, JHH = 8.88 Hz, 2H,
1
(
d, C, JCP = 7.1 Hz) ppm; 3 P{ H} NMR (CDCl
1
1
3
): d = 159.6 ppm;
2 2
Cl ); MS (CI, 80 eV): calculated:
2
D
0
½
a
5
ꢁ
¼ þ14:6 (c 0.772, CH
+
14.6; found: 515.3 [M ].
3
1
1
0
Ar-H) ppm;
PRh = 161.7 Hz) ppm; MS (ESI, pos): calculated: 725.6, found:
25.0.
2 2
P{ H} NMR (CD Cl , 162 MHz): d = 162.6 (d,
4
5
.2.3. (R
a
)-2,2 -Bis((2R,5R)-2,5-dimethylphospholan-1-yloxy)-
0
0
0
0
0
J
7
,5 ,6,6 ,7,7 ,8,8 -octahydro-1,1 -binaphthyl L3
The title compound was obtained by the procedure described
above using (R )-5,5 ,6,6 ,7,7 ,8,8 -octahydro-1,1 -binaphthyl-2,2 -
a
0
0
0
0
0
0
diol (333 mg, 1.13 mmol) as the diol. The product was obtained
as a colourless solid after filtration over basic alumina which can
be used without further purification. (428.6 mg, 81%); H NMR
4.3.2. [Rh(cycloocta-1,5-diene)L2]BF
The title compound was obtained by the procedure described
above using HBF O (0.077 mmol, 33 L), (acetylacetonato)-
ꢂEt
(1,5-cyclooctadiene)-rhodium (I) (24.1 mg, 0.077 mmol) and L2
4
1
4
2
l
(
0
(
CDCl
.90–1.05 (dd, JHH = 7.71 Hz, JPH = 18.82 Hz, 6H, CH
m, 1H, CH); 1.24–1.33 (m, 2H, CH ); 1.39–1.83 (m, 14H, CH
CH); 1.86–1.99 (m, 2H, CH ); 2.00–2.13(m, 2H, CH ); 2.20–2.31
m, 2H, CH ); 2.61–2.69 (m, 4H, CH ); 6.78 (d, JHH = 8.20 Hz,
H, Ar-H); 6.87 (d, JHH = 8.30 Hz, 2H, Ar-H) ppm;
3
): d = 0.82 (dd,
J
HH = 7.00 Hz,
J
PH = 11.41 Hz, 6H, CH
3
);
1
3
); 0.96–1.05
(40.0 mg, 0.077 mmol); (47.4 mg; 75%);
d = 0.57 (dd, JHH = 7.55 Hz, JHP = 20.45 Hz, 6H, CH
2H, CH); 1.62 (dd, JHH = 6.62 Hz, JPH = 13.88 Hz, 8H, CH
1.81–1.93 (m, 2H, CH ); 1.93–2.14 (m, 6H, CH); 2.18–2.54 (m, 8H,
CH); 4.64–4.73 (m, 2H, CH); 5.41–5.49 (m, 2H, CH); 7.07 (d,
H
NMR (CD
); 1.04–1.17 (m,
, CH);
2 2
Cl ):
2
2
,
3
2
2
3
(
2
2
.
1
3
2
C NMR
) 23.4 (d,
); 35.2 (d,
); 40.4 (d, JCP = 12.9 Hz,
CH); 42.4 (d, JCP = 19.4 Hz, CH); 114.4 (d, JCP = 16.7 Hz, C); 128.2
s, C); 128.4 (s, C); 130.2 (s, C); 136.6 (s, C); 152.6 (d,
(
CDCl
3
): d = 12.7 (s, CH
3
); 17.4 (s, CH
3
); 17.7 (s, CH
2
J
J
J
HH = 8.92 Hz, 2H, Ar-H); 7.28 (t, JHH = 7.65 Hz, 2H, Ar-H); 7.42 (d,
HH = 8.95 Hz, 2H, Ar-H); 7.47 (t, JHH = 7.58 Hz, 2H, Ar-H); 7.97 (d,
HH = 8.14 Hz, 2H, Ar-H); 8.08 (d, JHH = 8.94 Hz, 2H, Ar-H) ppm;
2
J
CP = 2,7 Hz, CH
2
); 27.6 (s, CH
2
); 29.6 (s, CH
2
J
CP = 2.8 Hz, CH ); 35.5 (d, JCP = 2.6 Hz, CH
2
2
3
1
1
2 2
P{ H} NMR (CD Cl ): d = 175.0 (d, JPRh = 170.6 Hz) ppm; MS
(
(ESI, pos): calculated: 725.6, found: 725.0.