D. Carmichael et al.
A
N
U
A
(br, 1H; CH), 4.52 (br, 1H; CH), 3.36 (t, J=16.2 Hz, dd, J
23.0 Hz, J(P,H)=1.1 Hz , 1H; PCCHHPPh2), 2.96 (ddd, J(P,H)=6.1 Hz,
(P,H)=4.2 Hz , J(H,H)=16.2 Hz, 1H; PCCHHPPh2), 2.70–2.20 (m, 7H;
A
N
G
G
ACHTREUNG
J
G
J
G
ACHTREUNG
A
ACHTREUNG
CH2, COD), 2.20 (s, 3H; Me), 2.19 (m, 1H; CH2, COD), 2.00 (s, 3H;
Me), 1.85 ppm (s, 15H; Cp*). Crystals suitable for the X-ray analysis
were obtained by diffusion of ether into an acetone solution of the race-
mic compound, prepared similarly from a mixture of 9 and 9a.
Data for (RRc,SP)-16: [a]2D5 =+1408 (c=1.0 in CH2Cl2); 31P NMR
1
(120 MHz, CDCl3, 258C): d=28.6 (br), ꢀ31.3 ppm; H (CDCl3): d=7.25–
7.06 (m, 5H), 2.35 (ddd,
J
(H,H)=14.7 Hz,
J
(P,H)=31 Hz,
J
ACHTREUNG
11 Hz, 1H), 2.28(ddd,
J
A
G
ACHTREUNG
Synthesis of compound 19:
A
solution of [Rh
G
N
J
ACHTREUNG
0.10 mmol) in THF (2 mL) was cooled in an ice bath and treated with
fluoroboric acid diethyl etherate (55% HBF4 in Et2O, 14 mL, 0.10 mmol).
The darkened solution was stirred for 30 s and then further treated over
a period of 30 s with a solution of 14 (70 mg, 0.11 mmol) in THF (1 mL),
which caused a colour change to orange. The solvents were removed and
the orange solid was washed with hexane (20.5 mL). Crystals suitable
for the X-ray analysis were obtained by diffusion of diethyl ether into a
G
ACHTREUNG
U
N
ACHTREUNG
A
G
ACHTREUNG
G
ACHTREUNG
U
A
ACHTREUNG
solution of the compound in dichoromethane. 31P NMR (120 MHz,
THF, 258C): d=61.3 (dd, J(P,Rh)=138Hz, (P,P)=27.2 Hz), 36.7 ppm
(dd, J(P,Rh)=170 Hz, J
(P,P)=27.2 Hz); 1H NMR (300 MHz, [D6] ace-
A
ACHTREUNGJACHTREUNG
N
ACHTREUNG
A
J
ACHTREUNG
(%) for C28H43BP2Ru: C 60.76, H: 7.83; found: C 60.82, H 7.97. Mass
A
ACHTREUNG
(CI/NH3): m/z: 554.
tone, 258C): d=7.92–7.82 (m, 2H), 7.67–7.49 (m, 8H), 7.40–7.31 (m,
2H), 7.28–7.18 (m, 3H), 5.98 (br, 1H; CH), 5.53 (br, 1H; CH), 4.56 (br,
Synthesis of compound 17: Fluoroboric acid diethyl etherate (55% HBF4
in Et2O, 177 mL, 1.30 mmol) was added as rapidly as possible to a solu-
tion of 10 (500 mg, 1.10 mmol) in dichloromethane (25 mL) at 08C. The
solvent was evaporated under reduced pressure and the product 12 was
washed with ether (220 mL). A solution of nBuLi (0.90 mL of 1.6m in
hexane, 1.45 mmol) in hexane (5 mL) was added dropwise at ꢀ788C to a
solution of PtBu2H·BH3 (240 mg, 1.50 mmol) in THF (10 mL) and the
mixture was allowed to stir for 15 min. A suspension of the carbocation
prepared above in diethyl ether (15 mL) was then added by canula over
a period of 2 min. After warming to room temperature, the pale yellow
solution containing 17 (33%) and the reduction product 23 (62%) was
evaporated to dryness and purified by chromatography.
1H; CH), 4.48(br, 1H; C H), 3.30 (ddd, J
(H,H)=15.5 Hz, 1H; PCCHHPPh2), 2.74 (ddd,
(P,H)=9.4 Hz , J(H,H)=15.5 Hz, 1H; PCCHHPPh2), 2.60–2.10 (m, 8H;
CH2, COD), 2.01 (s, 3H; Me), 1.95 (s, 3H; Me), 1.74 ppm (s, 15H; Cp*);
13C NMR (75 MHz, [D6] acetone, 258C): d=136.4 (d, J
(P,C)=13.8Hz,
ipso-Ph), 135.1 (d, J(P,C)=11.6 Hz, o-PPh2), 133.7 (d, J(P,C)=10.8Hz, o-
PPh2), 132.6 (d, J(P,C)=2.5 Hz, m-PPh2), 132.5 (d, J(P,C)=2.3 Hz, m-
PPh2), 132.3 (d, J(P,C)=43.7 Hz, ipso-PPh2), 131.9 (d, J(P,C)=41.4 Hz,
ipso-PPh2), 130.3 (d, J(P,C)=3.7 Hz, o-Ph), 130.2 (s), 130.1 (s), 129.4 (s),
A
ACHTREUNG
J
A
A
A
A
G
ACHTREUNG
AHCTREUNG
A
ACHTREUNG
A
ACHTREUNG
A
ACHTREUNG
AHCTREUNG
127.7 (s), 98.8 (dd, J=9.2 Hz, J=6.9 Hz, CH, COD), 97.8(dd, J=9.2 Hz,
J=6.9 Hz, CH, COD), 97.1 (dd, J=12.6 Hz, J=9.2 Hz, CH, COD), 96.7
(dd, J=9.2 Hz, J=9.2 Hz, CH, COD), 93.6 (dd, J=17.2 Hz, J=8.0 Hz),
92.7 (ddd, J=32.2 Hz, J=12.6 Hz, J=4.6 Hz), 91.2 (Cp*), 90.9 (d, J=
6.9 Hz), 88.5 (dd, J=9.2 Hz, J=4.6 Hz), 31.7 (CH2, COD), 31.1 (CH2,
Data for (R)-17: [a]2D5 =+1748 (c=1.0, DCM); 31P NMR (120 MHz,
CDCl3, 258C): d=45.8(br), ꢀ28.3 ppm; 1H NMR (300 MHz, CDCl3,
258C): d=7.24–7.16 (m, 4H), 7.15–7.07 (m, 1H; p-Ph), 2.58(ddd,
COD), 30.7 (CH2, COD), 30.3 (CH2, COD), 26.7 (dd, J
(P,C)=26.4 Hz, CH2PPh2), 13.3 (d, 2.3 Hz, Me), 12.9 (d, 3.4 Hz, Me),
10.7 ppm (Cp*).
A
A
G
J
G
J
ACHTREUNG
A
A
C
A
ACHTREUNG
AHCTREUNG
ACHTREUNG
Synthesis of compound 20: The complex was prepared and isolated as for
21 below, but was characterised by 31P NMR spectroscopy only. 31P NMR
A
ACHTREUNG
AHCTREUNG
(120 MHz, [D8] THF, 258C): d=66.5 (dd,
J
(P,Rh)=135 Hz,
J(P,P)=
N
A
G
U
ACHTREUNG
27 Hz), 33.6 ppm (dd, J(P,Rh)=170 Hz, J(P,P)=27 Hz).
G
ACHTREUNG
A
G
ACHTREUNG
Synthesis of compound 21: Compound 16, (31.4 mg, 0.057 mol) in di-
chloromethane (3 mL) was treated with fluoroboric acid diethyl etherate
(55% HBF4 in Et2O, 8 mL, 0.059 mmol) and the mixture was stirred for
J
G
G
N
ACHTREUNG
A
J
U
J
ACHTREUNG
(PCCMe), 13.6 (PCCMe), 10.7 (Cp*); CI-MS: m/z (%): 595 (100), 437
4 h at room temperature.
A
solution of [Rh
G
N
(28).
0.057 mmol) in THF (1 mL) was then cooled to 08C and treated with flu-
oroboric acid diethyl etherate (55% HBF4 in Et2O, 8 mL, 1 equiv). The
darkened solution was stirred for 2 min and then treated dropwise at
ꢀ788C with the solution of deboronated 16·HBF4 prepared above
(0.057 mmol) over a period of 5 mins. The resulting deep yellow solution
was allowed to warm to room temperature over 15 min and was then
evaporated to dryness under reduced pressure. Successive washes with di-
ethyl ether (32 mL) furnished the product as an orange-red solid.
Data for (S)-23: [a]D25 =+2178 (c=1.0 in CH2Cl2); 31P (CDCl3): d=
33.9 ppm; 1H (CDCl3): d=7.25–7.16 (m, 4H), 7.15–7.06 (m, 1H; p-Ph),
1.97 (s, 3H; MeCCPh), 1.87 (s, 3H; MeCCMe), 1.73 (s, 15H), 1.67 (d,
A
(P,H)=9.9 Hz, 3H; PCMe); 13C (CDCl3): d=139.6 (d, J
ACHTREUNG
ipso-Ph), 129.7 (d, J
100.0 (d, J
ACHTREUNG
G
ACHTREUNG
J
J
ACHTREUNG
31P NMR (120 MHz, [D8] THF, 258C): d=62.8(dd,
(P,P)=24 Hz), 35.8ppm (dd, (P,Rh)=171 Hz,
((CD3)2CO): d=64.4 (dd, J(P,Rh)=131 Hz, J(P,P)=23.8Hz), 37.0 ppm
(dd, J(P,Rh)=171 Hz, J
(P,P)=23.8Hz); 1H NMR (300 MHz, [D6] ace-
J
(P,Rh)=131 Hz,
ACHTREUNG
A
G
J
A
J
(P,P)=24 Hz); 31P
C23H29PRu: C 63.14, H 6.68; found: C 61.63, H 6.79; CI-MS: m/z (%):
438(100).
A
ACHTREUNG
A
ACHTREUNG
Synthesis of compound 18:
A
A
U
tone, 258C): d=7.42–7.24 (m, 5H; Ph), 5.89 (br, 1H; CH), 5.79 (br, 1H;
CH), 5.71 (br, 1H; CH), 5.03 (br, 1H; CH), 2.63–2.31 (m, 6H; CH2,
COD), 2.22–2.10 (m, 2H; CH2, COD), 2.13 (s, 3H; Me), 1.96 (s, 3H;
0.17 mmol) in THF (2 mL) was cooled to 08C and treated with fluorobor-
ic acid diethyl etherate (55% HBF4 in Et2O, 23 mL, 0.17 mmol) to give a
deep yellow-orange solution. After stirring for 30 s this mixture was
treated over a period of 30 s with a solution of 13 (100 mg, 0.17 mmol) in
THF (1 mL) and the mixture was stirred at room temperature for 10 min.
The solvents were removed and the red solid was washed with hexane
(20.5 mL) to give compound 18 (135 mg, 90%). 31P NMR (120 MHz,
Me), 1.88 (s, 15H; Cp*), 1.60 (d, J
(P,H)=14.2 Hz, PC
(CH3)3); 13C NMR (75 MHz, [D6] acetone, 258C):
d=136.5 (d, J(P,C)=13.0 Hz, ipso-Ph), 130.8(d, (P,C)=4.7 Hz, o-Ph),
129.2 (m-Ph), 127.9(p-Ph), 95.8(dd, (P,C)=8.2 Hz, J(C,Rh)=8.6 Hz,
CH, COD), 95.1 (dd, J(P,C)=13.2 Hz, , J(C,Rh)=8.1 Hz, CH, COD),
93.7 (dd, J(C,Rh)=1.1 Hz, J(P,C)=12.6 Hz, PCC), 93.6 (dd, J(P,C)=
8.2 Hz, (C,Rh)=6.9 Hz, CH, COD), 92.3 (dd, J(P,C)=8.6 Hz, J(C,Rh)=
7.8Hz, CH, COD), 92.0 (dd, J(P,C)=18Hz, J(C,Rh)=4.2 Hz, PCC), 91.5
A
A
G
ACHTREUNG
A
J
ACHTREUNG
A
J
A
ACHTREUNG
A
ACHTREUNG
[D8] THF, 258C): d=62.3 (dd,
J
(P,Rh)=137 Hz,
J(P,P)=25.7 Hz),
N
24.0 ppm (dd, J(P,Rh)=170 Hz, J
N
N
A
N
ACHTREUNG
[D6] acetone, 258C): d=7.90–7.81 (m, 2H), 7.70–7.48 (m, 7H), 7.42–7.40
(m, 4H), 7.36–7.26 (m, 2H), 6.30 (br, 1H; CH), 5.83, (br, 1H; CH), 4.83
A
G
A
ACHTREUNG
A
ACHTREUNG
5500
ꢁ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2007, 13, 5492 – 5502