3
2
56
R. W u¨ nsch et al. / Journal of Organometallic Chemistry 621 (2001) 352–358
3
4
1
2
5
6
J(HH)=14.7, J(HH)=3.0, J(HP)=3.0, 1H, H ],
.96 (s, 3H, OCH ), 2.06 (s, 3H, OCH ), 2.15–2.23 [dt,
1H, H ), 1.15 (m, 1H, H ), 5,30 (m, 1H, H ), 4.93 (m,
4
3
1
1H, H ), 6.05 (m, 1H, H ), 7.18–7.73 (m, 20H, Ph).
3
3
2
3
4
2
III
1
J(HH)=14.7, J(HH)=12.8, J(HP)=4.4, 1H, H ],
11 : l 1.06 (m, 1H, H ), 1.05 [s, 3H, C(CH ) ], 1.23 [s,
3H, C(CH ) ], 1.91 (s, 3H, OCCH ), 2.00 (s, 3H,
3
2
2
4
3
2
.46 [t, J(HH)=14.7, J(HP)=14.7, J(HP)=69, 1H,
3 2 3
2
5
2
3
6
5
H ], 3.35 [d, J(HH)=14.4, J(HPt)=23, 1H, H ], 4.85
OCCH ), 2.78 (m, 1H, H ), 2.46 (m, 1H, H ), 3.29 (m,
3
3
3
4
6
3
4
[
dt, J(HH)=9.5, J(HH)=2.2, 1H, H ], 6.22–6.25
1H, H ), 4.68 [ddd, J(HH)=11.1/9.4/8.8, 1H, H ],
3
II
3
3
(
m, 1H, 2-H ), 7.08–7.66 (m, 30H, Ph). 10 : l 1.72–
6.05 [m, J(HH)=9.4/11.1, 1H, H ], 7.18–7.73 (m,
20H, Ph). 11 : l 1.26 (m, 1H, H ), 0.68 [s, 3H,
2
3
4
IV
1
1
1
.77 [dt, J(HH)=12.5, J(HH)=3.7, J(HP)=3.7,
H, H ], 1.99 (s, 3H, OCH ), 2.10 (s, 3H, OCH ), 2.77
1
C(CH ) ], 1.15 [s, 3H, C(CH ) ], 1.93 (s, 3H, OCCH ),
3
3
3 2
3 2
3
2
4
3
2
[
dd, J(HH)=11.7, J(HP)=5.0, J(HPt)=51, 1H,
2.03 (s, 3H, OCCH ), 2.71 (m, 1H, H ), 2.40 (m, 1H,
3
2
2
3
4
5
6
4
H ], 2,93 [ddd, J(HH)=15.2, J(HH)=2.9, J(HP)=
H ), 3.32 (m, 1H, H ), 4.75 (m, 1H, H ), 6.03 (m, 1H,
H ), 7.18–7.73 (m, 20H, Ph). P{ H}-NMR (CH Cl ):
3
5
2
3
31
1
1
1.7, J(HPt)=103, 1H, H ], 5.20 [dt, J(HH)=15.4,
2 2
3
4
3
6
I
1
2
J(HH)=3.7, J(HP)=3.7, J(HPt)=54, 1H, H ],
11 : l 0.29/5.30, J(PPt)=2268/2785, J(PP)=32.4.
3
3
4
II
1
2
5
6
.05 [dt, J(HH)=9.5, J(HH)=2.9, 1H, H ], 6.26–
.31 (m, 1H, H ). C{ H}-NMR (CD Cl ): l 10 : 20.81
11 : l −1.89/1.81, J(PPt)=2229/2780, J(PP)=35.2.
3
13
1
I
III
1
2
11 : l 1.60/2.54, J(PPt)=2034/3236, J(PP)=25.8.
2
2
3
IV
1
2
(
s, OCH ), 21.12 (s, OCH ), 18.12 [dd, J(CP)=5.8,
J(CP)=2.6, C–4], 51.01 (s, C-1), 70.21 (s, C-2), 73.54
11 : l 0.43/10.58, J(PPt)=2079/3275, J(PP)=22.4.
3
3
4
II
(
s, C-3), 169.82 (s, CO), 170.19 (s, CO). 10 : 21.08 (s,
3.5. [(R,R)-diop]-
¸
¹¹¹¹¹¹¹¹¹¹¹¹¹¹º
3
I–IV
OCH ), 21.23 (s, OCH ), 25.85 [d, J(CP)=6.4, C-4],
Pt[S(O)–CH –CH(OAc)–CH(OAc)–CH –S] (12
)
3
3
2
2
4
5
2.00 (s, C-1), 74.94 (s, C-3), 76,07 [dd, J(CP)=4.2,
5
3
J(CP)=2.3, J(CPt)=49.7 Hz, C-2], 169.97 (s, CO),
The reaction was carried out in an analogous way
3
1
1
1
70.24 (s, CO). P{ H}-NMR (CH Cl ): l 19.10/19.52,
using the corresponding thiosulfinte (R* ,R*,S*)-3 [10].
2
2
SO
1
1
2
31
J(PPt)=2402/2866,
J(PPt)=2283/3309, J(PP)=24.5. MS (pos-FAB), m/
J(PP)=31.6;
21.92/22.90,
The reaction was monitored by P{ H}-NMR spec-
1
2
31
1
troscopy for 30 min at 0°C; the P{ H}-NMR spec-
troscopy revealed formation of four diastereoisomers
I–IV. After stirring for additional 16 h at r.t. the
solvent was evaporated under vacuo and the resulting
solid was washed thoroughly with a 1:1 ether–hexane
solvent mixture to remove the excess of thiosulfinate 3.
After drying in vacuo the yellow product was identified
as a mixture of four diastereoisomers (10:10:1:1). Yield:
+
z (relative intensity%): 972 (13) [M+H] ; 954 (20)
1
6
+
+
[
M−H– O] ; 719 (100) [(Ph P) Pt] .
3 2
3
.4. [(R,R)-diop]-
¸
¹¹¹¹¹¹¹¹¹¹¹¹¹¹º
I–IV
Pt[S(O)–CH –CH(OAc)–CH(OAc)–CH –S] (11
)
2
2
8
1 mg (43%). M.p. 166–169°C. Anal. Calc. for
−
1
To a solution of 7 [14](144 mg, 0.2 mmol) in 10 ml of
C H O P PtS (946.0 g mol ): C, 49.52; H, 4.69; S,
39 44 7 2 2
toluene, a solution of thiosulfinate (R* ,R*,R*)-2 [10]
6.78. Found: C, 49.13; H, 4.78; S, 7.21%. IR: w(SO) 983
s cm . H-NMR (CD Cl ): 12 : l 0.54/1.00 (m, 1H,
SO
−
1
1
I/II
(
200 mg, 0.8 mmol) in 4 ml of toluene was injected at
2
2
1
0
°C. The starting beige solution became deep yellow
H ), 0.41/1.02/1.09/1.18 [s, 6H, C(CH ) ], 1.95/1.98/
1.99/2.06 (s, 6H, OCCH ), 2.20–2.30 (m, 1H, H ), 1.02
3
(m, 1H, H ), 5,22/5.40 (m, 1H, H ), 4.86–4.89 (m, 2H,
H ), 6.04–6.08/6.09–6.13 [m, J(HH)=11.5/8.7/2.9,
1H, H ), 7.18–7.73 (m, 20H, Ph). 12
1H, H ), 0.45/0.94/1.05/1.11 [s, 6H, C(CH ) ], 1.91/
1.93/2.00/2.03 (s, 6H, OCCH ), 2.25/2.75 (m, 1H, H ),
2.45–3.31 (m, 2H, H ), 4.60–4.62 (m, 2H, H ), 6.16–
6.21/6.26–6.31 [m, J(HH)=11.9/8.8/3.2 1H, H ],
7.18–7.73 (m, 20H, Ph). P{ H}-NMR (CH Cl ): 12 :
l 0.10/5.65, J(PPt)=2261/2808, J(PP)=32.6. 12 : l
−2.98/1.31, J(PPt)=2207/2764, J(PP)=35.2. 12 : l
3 2
31
1
2
and the reaction was monitored by P{ H}-NMR spec-
3
1
1
5
6
troscopy for 30 min at 0°C; the P{ H}-NMR spec-
troscopy revealed formation of four diastereoisomers
I–IV. After stirring for additional 16 h at r.t. the
solvent was evaporated under vacuo and the resulting
solid was washed thoroughly with a 1:1 ether–hexane
solvent mixture to remove the excess of thiosulfinate 2.
After drying in vacuo the yellow product was identified
as a mixture of two diastereoisomers (1:1). Yield: 95 mg
4
3
3
III/IV
: l 0.77 (m,
1
3
2
2
3
5
/6
4
3
3
3
1
1
I
2
2
1
2
II
(
51%).
M.p.
154–157°C.
Anal.
Calc.
for
−
1
1
2
III
C H O P PtS (946.0 g mol ): C, 49.52; H, 4.69; S,
3
9
44
7
2
2
1
2
IV
6
.78. Found: C, 50.03; H, 4.75; S, 7.08%. IR: w(SO) 983
1.10/1.98, J(PPt)=2071/3230, J(PP)=25.8. 12 : l
−
1
1
I
2
1
2
s cm . H-NMR (CD Cl ): 11 : l 0.94 [d, J(HH)=
−0.08/11.02, J(PPt)=2119/3268, J(PP)=22.7.
3.6. Reaction of complex 11 with dppe: Ph -
2
2
1
13.3, 1H, H ], 0.77 [s, 3H, C(CH ) ], 1.18 [s, 3H,
3 2
C(CH ) ], 1.98 (s, 3H, OCCH ), 2.00 (s, 3H, OCCH ),
3
2
3
3
¸¹¹¹¹¹¹¹º ¸¹¹¹¹¹¹¹¹¹¹¹¹º
2
2
5
6
2
5
(
.13 (m, 1H, H ), 1.05 (m, 1H, H ], 5,20 (m, 1H, H ),
.00 [dt, J(HH)=10.1, J(HH)=5.0, 1H, H ], 5.97
P(CH ) PPh –Pt[S(O)–CH –CH(OAc)–CH(OAc)–CH –S
2 2 2 2 2
3
3
4
(13)
3
II
m, 1H, H ), 7.18–7.73 (m, 20H, Ph). 11 : l 1.15 (m,
1
1
H, H ), 1.13 [s, 3H, C(CH ) ], 1.23 [s, 3H, C(CH ) ],
Complex 11 (95 mg, 0.1 mmol) (1:1 mixture of two
3
2
3 2
1
.95 (s, 3H, OCCH ), 2.06 (s, 3H, OCCH ), 2.20 (m,
diastereoisomers) in 10 ml of dichloromethane was
3
3