Donohoe et al.
reaction; these may be virtually undetectable by standard
analytical techniques.
(0.15 g, 75%) as a separable 1:1 mixture of stereoisomers.
Stereoisomer R: 1H NMR (400 MHz, CDCl
) δ 7.44-6.88 (m, 26
3
H), 6.82-6.79 (m, 2 H), 6.67 (q, J ) 6.8, 1 H), 6.54-6.51 (m, 2
H), 5.92 (q, J ) 6.8, 1 H), 5.72 (d, J ) 9.2, 1 H), 5.24-5.19 (m,
Experimental Section
2
H), 4.59 (s, 1 H), 1.99 (d, J ) 6.8, 3 H), 1.38 (d, J ) 7.2, 3 H);
C NMR (100 MHz, CDCl ) δ 144.7, 143.5, 143.0, 141.8, 141.6,
3
1
3
Osmium(VI) Complex 7. Method 1: A solution of osmi-
um(VIII) complex 2 (0.18 g, 0.51 mmol) and E-stilbene (0.46 g,
140.3, 128.8, 128.3, 128.3, 128.1, 128.0, 127.9, 127.9, 127.8, 127.7,
127.5, 127.3, 127.2, 127.2, 127.0, 127.0, 126.8, 126.6, 126.4, 97.1,
2
.6 mmol) in dry CH
The reaction mixture was evaporated under reduced pressure, and
the product was isolated by flash column chromatography (SiO
petrol f petrol-Et O, 80:20) to furnish 7 as a red solid (0.22 g,
2%). Method 2: 1,2-Diphenyl-1,2-N,N-di-tert-butylamine (0.02
2 2
Cl (20 mL) was heated at reflux for 70 h.
1
96.6, 86.8, 81.2, 67.8, 65.8, 23.5, 18.2. Stereoisomer â: H NMR
2
,
3
(400 MHz, CDCl ) δ 7.42-6.86 (m, 29 H), 6.32-6.30 (m, 2 H),
6.08 (q, J ) 6.8, 1 H), 5.72 (d, J ) 9.2, 1 H), 5.35 (s, 1 H), 5.22
(d, J ) 9.6, 1 H), 4.88 (s, 1 H), 1.59 (d, J ) 6.8, 3 H), 1.53 (d, J
2
5
) 6.8, 3 H); 13C NMR (100 MHz, CDCl
g, 0.06 mmol) was subjected to procedure B with E-stilbene. The
reaction furnished 8 (1:1 mixture of stereoisomers) as an orange
solid (0.02 g, 39%) and 7 as a red solid (0.01 g, 22%): 1H NMR
3
) δ 145.1, 143.8, 142.1,
141.3, 140.7, 140.5, 129.3, 128.6, 128.3, 128.2, 128.1, 127.9, 127.7,
127.6, 127.6, 127.6, 127.3, 127.2, 127.1, 127.0, 126.9, 126.5, 125.4,
97.0, 96.8, 87.5, 82.0, 69.2, 66.8, 18.9, 16.7; IR (KBr disk) 2929,
(
1
8
400 MHz, CDCl
3
) δ 7.36-7.25 (m, 10 H), 4.99 (s, 2 H), 1.23 (s,
8 H); 13C NMR (100 MHz, CDCl
7.6, 68.8, 31.1; IR (KBr disk) 2970, 1740, 1464, 1452, 893 cm
-1
) δ 147.0, 129.2, 128.1, 126.7,
1494, 1453, 923 cm ; ESIMS m/z (rel intensity) 897 (100%, M
3
-
1
+
+
192
;
+ CH
3
CN + NH
4
), 839 (100%, M + H ); C44
H N O
43 2 3
Os
+
+
ESIMS m/z (rel intensity) 1112 (100%, 2M + NH
O
1
4
); C22H
31
N
2
-
requires M + H 839.2889, found M + H 839.2896.
1
92
+
Os requires M + H 547.2000, found M + H 547.2004; mp
Osmium Intermediate 15. Diamine 14 (0.038 g, 0.13 mmol)
was subjected to procedure B with E-stilbene. The reaction
furnished 15 as an amorphous orange solid (0.08 g, 86%) as a 1:1
2
55-158 °C.
Osmium Intermediate 8. E-Stilbene (0.026 g, 0.14 mmol) was
1
subjected to procedure A (see Supporting Information) with
osmium(VI) reagent 7. Compound 8 was furnished as an orange
solid (0.05 g, 92%) as a 1:1 mixture of stereoisomers. Spectroscopic
mixture of stereoisomers. Spectroscopic data for the mixture:
NMR (400 MHz, CDCl
H
3
) δ 7.37-7.08 (m, 10 H), 5.87, 5.86 (2 ×
d, J ) 10.4, 1 H), 5.55-5.51 (m, 1.5 H), 5.43 (d, J ) 10.4, 0.5 H),
4.91, 4.82 (2 × d, J ) 9.0, 1 H), 4.47-4.36 (m, 1 H), 4.24-4.03
(m, 3 H), 3.73, 3.73, 3.67, 3.42 (4 × s, 6 H), 2.60-2.43 (m, 2 H),
data for the mixture: 1H NMR (400 MHz, CDCl
) δ 7.52-7.50
3
(
m, 2 H), 7.40-7.23 (m, 16 H), 6.96-6.92 (m, 2 H), 6.01, 5.96 (2
×
s, 1 H), 5.62, 5.55 (2 × d, J ) 10.0, 1 H), 5.17-4.94 (m, 2 H),
1.11-1.01 (m, 7.5 H), 0.93, 0.80, 0.67 (3 × d, J ) 6.4, 4.5 H);
13
13
1
.45, 1.41 (2 × s, 9 H), 1.36, 1.34 (2 × s, 9 H); C NMR (100
3
C NMR (100 MHz, CDCl ) δ 174.6, 173.8, 172.0, 171.9, 141.5,
MHz, CDCl
3
) δ 149.5, 149.0, 145.9, 145.1, 141.3, 140.9, 128.8,
140.9, 140.8, 140.1, 128.1, 128.0, 127.9, 127.8, 127.7, 127.7, 127.6,
127.2, 126.9, 126.9, 97.4, 96.6, 95.9, 95.7, 76.5, 75.2, 74.7, 74.3,
61.7, 61.5, 61.4, 61.2, 51.8, 51.7, 51.3, 51.1, 32.1, 31.9, 28.0, 27.4,
20.5, 20.5, 20.3, 20.0, 19.8, 19.8, 18.9, 18.7; IR (KBr disk) 1734,
128.6, 128.3, 128.1, 128.0, 127.9, 127.7, 127.6, 127.5, 127.2, 127.1,
126.9, 126.9, 126.3, 98.1, 97.3, 96.5, 92.6, 89.5, 87.9, 82.1, 82.0,
6
9.9, 69.6, 69.5, 68.4, 31.7, 31.4, 30.9, 30.2; IR (KBr disk) 2972,
-
1
-1
+
1600, 1451, 906 cm ; ESIMS m/z (rel intensity) 1485 (15%, 2M
941 cm ; ESIMS m/z (rel intensity) 729 (20%, M + Na ), 707
+
+
192
+
192
+
7
H ), 743 (100%, M + H ); C36
H
43
N O
2 3
Os requires M + H
(100%, M + H ); C28
found M + H 707.2368.
N,N′-Diphenylethylenediamine 18. Triethylamine (0.77 mL, 5.5
H
39
N
2
O
7
Os requires M + H 707.2372,
+
+
43.2889, found M + H 743.2896; mp 132-135 °C.
Osmium Intermediate 9. E-Octene (0.023 mL, 0.12 mmol) was
subjected to procedure A with osmium(VI) reagent 7. Compound
mmol) was added dropwise to a solution of aniline (0.25 mL, 2.8
9
was furnished as an amorphous orange solid (0.04 g, 96%) as a
2 2
mmol) in CH Cl (20 mL) and cooled to -78 °C. Oxalyl chloride
1
:1 mixture of stereoisomers. Spectroscopic data for the mixture:
(0.11 mL, 1.3 mmol) was added dropwise and stirred at room
temperature for 20 h. The precipitate was filtered off, and the
solution was evaporated under reduced pressure. The product was
1
H NMR (400 MHz, CDCl
m, 6 H), 6.83-6.80 (m, 2 H), 5.83, 5.78 (2 × s, 1 H), 4.90, 4.84
2 × s, 1 H), 4.58-4.50 (m, 0.5 H), 4.32-4.24 (m, 1 H), 4.00-
.90 (m, 0.5 H), 1.82-1.40 (m, 8 H), 1.37-1.31 (m, 18 H), 1.02
3
) δ 7.48-7.45 (m, 2 H), 7.37-7.21
(
(
2 2 2
isolated by flash column chromatography (SiO , CH Cl ) to furnish
1
3
N,N′-diphenyloxalamide as a white solid (0.17 g, 55%): H NMR
(400 MHz, DMSO) δ 10.84 (br s, 2 H), 7.87 (d, J ) 7.7, 4 H),
7.38 (app. t, 4 H), 7.16 (t, J ) 7.4, 2 H); 13C NMR (100 MHz,
DMSO) δ 159.4, 138.5, 129.6, 125.5, 121.3; IR (KBr disk) 3307,
t, J ) 6.8, 6 H); 1 C NMR (100 MHz, CDCl
3
(
3
) δ 149.7, 149.7,
1
1
6
2
+
45.5, 145.2, 128.8, 128.5, 128.1, 128.0, 127.6, 127.4, 127.4, 127.1,
27.0, 126.7, 126.5, 126.4, 89.3, 88.6, 81.9, 81.9, 68.9, 68.5, 68.4,
7.9, 37.6, 35.7, 31.5, 30.6, 30.4, 29.9, 19.8, 18.8; IR (KBr disk)
-
1
+
1662, 1437 cm ; CIMS m/z (rel intensity) 258 (45%, M + NH
4
),
-
1
+
960, 1452, 910 cm ; ESIMS m/z (rel intensity) 675 (100%, M
241 (100%, M + H ); C14
M + H 241.0968; mp 235-236 °C.
H
13
N
2
O
2
requires M + H 241.0977, found
+
192
+
H ); C30
H
47
N O
2 3
Os requires M + H 675.3202, found M +
+
H
675.3225.
Lithium aluminum hydride (0.16 g, 4.2 mmol) was then added
to a solution of N,N′-diphenyloxalamide (0.17 g, 0.69 mmol) in
dry THF (15 mL) and heated at reflux for 18 h. The reaction mixture
Osmium Intermediate 10. Cyclohexene (0.017 mL, 0.17 mmol)
was subjected to procedure A with osmium(VI) reagent 7.
Compound 10 was furnished as an orange solid (0.05 g, 96%) as
a 2:1 mixture of stereoisomers. Spectroscopic data for the mix-
was quenched with 1 M NaOH, extracted with CH
(MgSO ), and evaporated under reduced pressure, and the product
was purified by flash column chromatography (SiO , CH Cl -petrol,
5:4) to furnish 18 as a white solid (0.13 g, 87%). The spectroscopic
Cl
2 2
(× 3), dried
4
ture: 1H NMR (400 MHz, CDCl
) δ 7.49-7.24 (m, 9 H), 6.98-
.96 (m, 1 H), 5.82 (s, 1 Hminor), 5.74 (s, 1 Hmajor), 4.96-4.85 (m,
major and 1 H), 4.61-4.56 (m, 1 Hminor), 4.48-4.45 (m, 1 Hminor),
.33-2.20 (m, 1 H), 2.08-1.96 (m, 3 H), 1.81-1.20 (m, 22 H);
3
2
2
2
6
2
2
3
1
H
data for this compound matched that in the literature.
N,N′-Bis(2,6 dichlorophenyl)ethylenediamine 19. Sodium hy-
dride, 60% dispersion in mineral oil (0.729 g, 18.2 mmol), was
added to a solution of 2,6-dichloroaniline (1.23 g, 7.59 mmol) in
dry THF (15 mL) at 0 °C and cooled to -78 °C. A solution of
oxalyl chloride (0.07 mL, 0.85 mmol) in dry THF (5 mL) was added
dropwise and stirred at room temperature for 50 h. The reaction
was quenched with cold water, and the THF was evaporated under
13
3
C NMR (100 MHz, CDCl ) δ 149.9, 149.8, 145.0, 144.9, 128.6,
128.5, 128.2, 127.7, 127.4, 127.1, 127.0, 126.7, 126.7, 126.3, 89.9,
89.5, 87.5, 86.7, 84.8, 82.5, 82.2, 81.9, 69.5, 69.3, 69.2, 68.7, 31.7,
31.6, 31.2, 30.9, 30.7, 30.3, 30.0, 28.5, 23.5, 22.8, 21.2, 21.1; IR
-
1
(KBr disk) 2932, 1740, 1450, 907 cm ; ESIMS m/z (rel intensity)
+
192
6
45 (100%, M + H ); C28
H N O
41 2 3
Os requires M + H 645.2732,
+
found M + H 645.2736; mp 130-131 °C.
reduced pressure. The product was extracted with CH
dried (MgSO ), evaporated under reduced pressure, and isolated
by flash column chromatography (SiO , CH Cl ) to furnish N,N′-
bis(2,6-dichlorophenyl)oxalamide as a white solid (0.37 g, 32%):
2
Cl
2
(× 3),
Osmium Intermediate 13. Diamine 12 (0.10 g, 0.24 mmol) was
subjected to procedure B (see Supporting Information) with
E-stilbene. The reaction furnished 13 as an amorphous orange solid
4
2
2
2
4488 J. Org. Chem., Vol. 71, No. 12, 2006