W. Baratta et al.
broaden the scope of these complexes for other catalytic
transformations, including hydrogen-borrowing reactions,
through alcohol activation.
120.0 (m, aromatic carbons), 78.3 (d, J
(C,P)=8.4 Hz; C ), 76.1 (d, J(C,P)=2.9 Hz; C
.9 Hz; C ), 73.2 (d, J(C,P)=5.8 Hz; C ), 70.6 (d, J
), 70.1 (d, J(C,P)=5.5 Hz; C ), 69.9 (d, J(C,P)=5.6 Hz; C
2.2 ppm (d, J(C,P)=2.6 Hz; CH ); P{ H} NMR (81.0 MHz, CD
08C): d=57.8 (d, J(P,P)=35.6 Hz), 44.2 ppm (d, J(P,P)=35.6 Hz); ele-
FeN Ru: C 57.57, H 4.35, N
A
T
N
R
N
U
G
5
H
4
), 77.6 (d, J-
A
T
G
R
N
U
G
5
H
4
A
H
U
G
E
N
G
5
H
4
ACHTUNGTRENNUNG( C,P)=
5
H
4
A
H
U
T
E
U
5
H
4
ACHTUNGTRENNUNG
5
H
4
A
H
U
G
R
N
U
G
5
H
4
3
A
H
U
G
R
N
U
G
5 4
H
1
1
A
H
U
T
E
N
N
2
2
2
,
A
H
U
G
R
N
U
G
ACHTUNGTRENNUNG
mental analysis calcd (%) for C40
.36; found: C 57.14, H 4.25, N 3.17.
Synthesis of trans-[RuCl (dppb)(ae)] (10): [RuCl
.174 mmol) and 2-aminoethanol (12 mL, 0.200 mmol) were treated with
H
36Cl
2
2 2
P
Experimental Section
3
2
A
H
U
G
E
N
N
2 3
ACHTUNGERTUNNNG( dppb) ACTHUNGTERNNUG(N PPh )] (150 mg,
General: All reactions were carried out under an argon atmosphere by
using standard Schlenk techniques. The solvents were carefully dried by
standard methods and distilled under argon before use. The diphos-
phanes, the nitrogen ligands, and all other chemicals were purchased
from Aldrich and Strem and used without further purification. The com-
0
toluene (2.0 mL). The suspension was stirred for 2 h at 608C and concen-
trated to 0.5 mL. Addition of heptane (2 mL) afforded a yellow precipi-
tate, which was washed with heptane (3ꢄ1 mL) and diethyl ether (3ꢄ
1
1
mL) and dried under reduced pressure. Yield: 98 mg (85%); H NMR
[
24]
[25]
[26]
pounds [MCl
2
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
(PPh
4,
3
)
3
] (M=Ru,
Os ), [RuCl
2
A
H
U
G
R
N
N
(dppb)
A
H
U
G
R
N
U
(PPh
3
)],
and
(
200.1 MHz, CD
2
Cl
.86 (br s, 2H; CH
.69 (br s, 6H; CH
2
, 208C): d=7.69–7.18 (m, 20H; aromatic protons),
OH), 3.53 (br s, 1H; OH), 2.93 (br s, 2H; CH N),
P, NH ), 1.65 (br s, 2H; CH CH P), 1.56 ppm (br s,
P); P{ H} NMR (81.0 MHz, CD Cl , 208C): d=59.5 (d, J-
(P,P)=42.7 Hz); elemental analysis calcd
Ru: C 54.63, H 5.35, N 2.12; found: C 54.38, H
[
15a]
[16b]
[16a]
[16b]
[27]
[10]
[17]
1
,
2,
3,
6, 7, and 13 were prepared according to the
3
2
2
2
2
literature procedure. NMR measurements were recorded on a Bruker
AC 200 spectrometer and the chemical shifts, in ppm, are relative to
2
2
2
2
31
1
H; CH
2
CH
2
2
2
1
13
1
31
1
TMS for H and C{ H}, and 85% H
3 4
PO for P{ H}. Elemental analyses
ACTHNGUTRENNU(G P,P)=42.7 Hz), 44.4 ppm (d, J CAHTUNGTRENNNUG
(
(
C, H, N) were carried out with a Carlo Erba 1106 elemental analyzer,
%) for C30
H
35Cl
2
NOP
2
whereas the GC analyses were performed with a Varian GP-3380 gas
chromatograph.
5
.61, N 2.15.
Synthesis of [OsCl
.143 mmol) and dppb (70 mg, 0.164 mmol) were treated with mesitylene
2.0 mL) and the suspension was stirred for 2 h at room temperature.
2 2 3 3
ACHTUNGENTRNUNG( dppb)(trans-dach)] (11): [OsCl AHCTUNGTRENNUG( PPh ) ] (150 mg,
2 2 3
Synthesis of trans-[RuCl ACHUTNGTRENNUNG( dppb)(trans-dach)] (5): [RuCl ACHTUGNRTNEUNG( dppb) AHCUNTGTRENNUGN( PPh )]
0
(
(
1
100 mg, 0.116 mmol) and (Æ)-trans-diaminocyclohexane (trans-dach;
3.9 mL, 0.116 mmol) were dissolved in dichloromethane (2.0 mL) and
Trans-dach (18 mL, 0.150 mmol) was added and the resulting suspension
was stirred at 1358C for 4 h and concentrated to 0.5 mL. Addition of hep-
tane (2 mL) afforded a dark-green precipitate, which was washed with
the solution was stirred for 24 h at room temperature. The resulting solu-
tion was concentrated (0.5 mL) and addition of heptane (2 mL) afforded
a yellow precipitate, which was washed with 1-propanol (3ꢄ1 mL) and
heptane (3ꢄ1 mL) and diethyl ether (3ꢄ1 mL) and dried under reduced
1
dried under reduced pressure. Yield: 68 mg (82%); H NMR
1
pressure. Yield: 72 mg (63%); H NMR (200.1 MHz, CD
2
Cl
, NH
(P,P)=13.4 Hz, major cis
(P,P)=13.4 Hz), À2.2 (d, J(P,P)=13.3 Hz, minor cis
2
, 208C): d=
2
); P{ H}
(
2
200.1 MHz, CDCl
.89 (m, 4H; CH
CH CH P, CH CH), 0.99 ppm (m, 4H; CH
CDCl , 208C): d=133.1–127.5 (m; aromatic carbons), 57.1 (s; CHNH
5.7 (s; CH CH), 24.4 (s; CH ), 24.3 (d, (C,P)=29.0 Hz; PCH
2.0 ppm (s; CH ); P{ H} NMR (81.0 MHz, CDCl
3
, 208C): d=7.71–7.26 (m, 20H; aromatic protons),
3
1
1
8
.00–6.90 (m; aromatic protons), 3.98–0.90 (m; CH, CH
NMR (81.0 MHz, CD Cl
, 208C): d=À2.7 (d, J
complex), À11.7 (d, J
2
2
P), 2.49 (m, 6H; CHN, NH ), 1.67–1.49 (m, 8H;
2
1
3
1
2
2
ACHTUNGTRENNUNG
2
2
2
2
); C{ H} NMR (50.3 MHz,
A
H
U
G
R
N
U
G
ACHTUNGTRENNUNG
3
2
),
),
complex), À12.8 (d, J(P,P)=13.3 Hz), À11.7 ppm (s; trans complex); ele-
A
H
N
R
N
U
G
3
2
2
2
JACHTUNGTRENNUNG
2
3
1
1
mental analysis calcd (%) for C34
found: C 49.96, H 5.44, N 3.48.
2 2 2
H42Cl N OsP : C 50.93, H 5.28, N 3.49;
2
3
, 208C): d=45.1 ppm
(
s); elemental analysis calcd (%) for C34
N 3.93; found: C 57.15, H 5.73, N 3.60.
Synthesis of trans-[RuCl (dppf)(ampy)] (8): [RuCl
.209 mmol) and dppf (127 mg, 0.229 mmol) were treated with toluene
2.0 mL) and the suspension was stirred for 1 h at 508C. After addition
H
42Cl
2
N
2
P
2
Ru: C 57.30, H 5.94,
2 2 3 3
Synthesis of trans- ACHTUNGRTENNGNU[ OsCl ACHTUNGTNERN(GU dppf)(trans-dach)] (12): [OsCl ACHTUNGTRENNUNG( PPh ) ]
(
200 mg, 0.191 mmol) and dppf (117 mg, 0.211 mmol) were treated with
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
2
A
H
U
G
R
N
U
G
A
H
U
G
R
N
U
G
2 3 3
ACHTUNGTRNENG(U PPh ) ] (200 mg,
toluene (3.0 mL) and the suspension was heated at reflux for 4 h. After
addition of trans-dach (23.0 mL, 0.191 mmol) the yellow suspension was
stirred for 24 h at RT and then concentrated to 0.5 mL. Addition of hep-
tane (2 mL) afforded a yellow precipitate, which was washed with hep-
0
(
of ampy (23 mL, 0.223 mmol) the suspension was stirred for 2 h at 508C
and then concentrated to about 0.5 mL. Addition of heptane (2 mL) af-
forded a yellow precipitate, which was washed with heptane (3ꢄ1 mL)
tane (3ꢄ1 mL) and diethyl ether (3ꢄ1 mL) and dried under reduced
1
pressure. Yield: 130 mg (73%); H NMR (200.1 MHz, CD
2
Cl
), 4.55 (s,
(H,H)=8.9 Hz, 2H; NH ), 2.86
), 2.61 (m, 2H; CH), 1.71 (m, 2H; CH ),
); C{ H} NMR (50.3 MHz,
2
, 208C):
and diethyl ether (3ꢄ1 mL) and dried under reduced pressure. Yield:
1
d=7.79–7.10 (m, 20H; aromatic protons), 4.60 (s, 2H; C
H; C ), 4.16 (s, 4H; C ), 3.10 (d, J
t, J(H,H)=9.0 Hz, 2H; NH
5 4
H
1
60 mg (92%); H NMR (200.1 MHz, CD
2
Cl
(H,H)=7.9 Hz, 4H; aromatic protons), 7.60–
.03 (m, 18H; aromatic protons), 6.58 (t, J(H,H)=6.6 Hz, 1H; aromatic
proton), 4.73 (m, 2H; C ), 4.31 (m, 2H; CH NH ), 4.22 (m, 2H;
), 4.14 (m, 2H; C ), 4.03 (m, 2H; C ), 3.05 ppm (m, 2H; NH );
C{ H} NMR (50.3 MHz, CD Cl , 208C): d=163.8 (m, NCCH ), 156.3
d, J(C,P)=3.7 Hz; NCH), 139.2–120.1 (m, aromatic carbons), 89.9 (dd,
(C,P)=46.0 and 4.9 Hz; ipso-C ), 82.4 (dd, J(C,P)=46.8 and 0.8 Hz;
ipso-C ), 77.9 (d, J(C,P)=7.7 Hz; C ), 75.7 (d, J(C,P)=7.1 Hz;
), 71.5 (d, J(C,P)=5.8 Hz; C ), 69.1 (d, J(C,P)=5.0 Hz; C ),
0.4 ppm (t, J(C,P)=2.3 Hz; CH ); P{ H} NMR (81.0 MHz, CD Cl
08C): d=51.6 (d, J(P,P)=38.3 Hz), 40.9 ppm (d, J(P,P)=38.3 Hz); ele-
FeN Ru: C 57.57, H 4.35, N
2
, 208C): d=8.51 (m, 1H; o-
2
5
H
4
5
H
4
A
H
U
G
R
N
U
2
5 4
C H N), 8.10 (pseudo t, JACTHNUTRGENNUG
(
1
A
H
U
G
R
N
N
2
2
7
ACHTUNGTRENNUNG
1
3
1
.47 (m, 2H; CH
Cl
matic carbons), 134.7 (t, J
(C,P)=4.9 Hz; aromatic carbons), 129.1–127.2 (m; aromatic carbons),
0.2 (dd, J(C,P)=60.9 and 5.6 Hz; ipso-C ), 76.5 (t, J(C,P)=3.9 Hz;
), 76.3 (t, J(C,P)=3.8 Hz; C ), 74.1 (br s; C ), 70.1 (s; C ),
7.9 (s; CHNH ), 35.6 (s; CH ), 25.0 ppm (s; CH ); P{ H} NMR
2
), 1.05 ppm (m, 4H; CH
2
5
H
4
2
2
CD
2
2
, 208C): d=140.9 (m; ipso aromatic carbons), 140.1 (m; ipso aro-
(C,P)=4.8 Hz; aromatic carbons), 134.3 (t, J-
C
5
H
4
5
H
4
5
H
4
2
1
3
1
ACHTUNGTRENNUNG
2
2
2
AHCTUNGTRENNUNG
(
ACHTUNGTRENNUNG
9
A
H
U
G
R
N
N
5
H
4
ACHTUNGTRENNUNG
J
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
5
H
4
ACHTUNGTRENNUNG
C
5
5
H
4
A
H
U
G
R
N
U
G
5
H
4
5
H
4
5 4
H
5
H
4
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
5
H
4
ACHTUNGTRENNUNG
3
1
1
2
2
2
C
5
2
5
H
4
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
5
H
4
3
A
H
U
G
R
N
U
G
5 4
H
1
1
(81.0 MHz, CD Cl , 208C): d=À9.9 ppm (s); elemental analysis calcd
2
2
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
2
2
2
,
(
%) for C40
H
42Cl
2
2 2
FeN OsP : C 51.68, H 4.55, N 3.01; found: C 50.96, H
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
ACHTUNGTRENNUNG
4
.63, N 2.87.
mental analysis calcd (%) for C40
.36; found: C 58.32, H 4.43, N 3.16.
Synthesis of cis-[RuCl (dppf)(ampy)] (9): Compound
.144 mmol) was treated with toluene (2.0 mL), stirred for 24 h at 1208C,
and then the suspension was dried under reduced pressure. Yield: 110 mg
H
36Cl
2
2 2
P
3
Procedure for the catalytic dehydrogenation of alcohols: The Ru or Os
complex (0.01 mmol) was dissolved in tBuOH (2 mL). After addition of
the alcohol substrate (2.5 mmol) and KOtBu (0.05 mmol) the solution
was heated at 1308C (bath temperature) under argon in an open system
and the conversion was determined by GC and NMR analyses, which re-
vealed the absence of side products (Ru or Os 0.4 mol%, KOtBu
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
2
A
H
U
G
E
N
N
A
H
U
G
R
N
U
G
8 (120 mg,
0
1
(
C
(
92%); H NMR (200.1 MHz, CD
N), 8.49 (pseudo t, J(H,H)=7.8 Hz, 2H; aromatic protons), 8.16
pseudo t, J(H,H)=8.1 Hz, 2H; aromatic protons), 7.64–6.70 (m, 18H;
aromatic protons), 6.56 (s, 1H; aromatic proton), 4.95 (m, 1H; C ),
), 3.96 (m,
), 3.09 (m,
2 2
Cl , 208C): d=8.91 (m, 1H; o-
5
H
4
ACHTUNGTRENNUNG
2
mol%).
ACHTUNGTRENNUNG
H
4
Procedure for the catalytic dehydrogenation of 3b-hydroxy steroids: The
ruthenium 7 or osmium 13 complex (0.01 mmol), the sterol substrate
(1.25 mmol), and KOtBu (0.05 mmol) were dissolved in tBuOH (2 mL)
and toluene (1 mL). The solution was heated at 1458C (bath tempera-
ture) under argon in an open system and the conversion into the 4-en-3-
5
4
1
1
.45 (m, 1H; C
H; C ), 3.77–3.58 (m, 3H; CH
H; CH N), 1.70 (m, 1H; NH ), 1.57 ppm (m, 1H; NH
5
H
4
), 4.22 (m, 1H; C
5
H
4
), 4.08 (m, 1H; C
5 4
H
5
H
4
2
N, C
5
H
4
), 3.32 (m, 1H; C H
5 4
1
3
1
2
2
2
); C{ H} NMR
2
, 208C): d=158.6 (m, NCCH ), 151.0 (s, NCH), 137.7–
(
50.3 MHz, CD
2
Cl
2
3480
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 3474 – 3481