Molecular Motors
FULL PAPER
+
hexylphosphane (3mg, 7.3 mmol, 0.5 equiv) and anhydrous
K
3
PO
4
TOF): m/z: 3348 [M] ; HR MALDI-TOF: m/z calcd for
+
+
(
28 mg, 0.132 mmol, 10 equiv) were added and the mixture was heated at
C
215
H
193BFe
5
N
6
O
6
Ru [M] : 3348.096; found: 3348.061 (100% [M] ); CV
À1
1
008C overnight. The crude reaction mixture was evaporated under
(CH
2
Cl
2
, nBu
4
NPF
6
; vs.SCE; sweep rate: 100 mVs ): EFeII/FeIII : +0.42 V
vacuum. The product was purified by column chromatography (SiO
2
:
rev (5e); ERuII/RuIII : +0.76 V rev (1e).
1
CH
CD
2
Cl
2
) to give 4 as a yellow solid (6 mg, 25%). H NMR (500 MHz,
): d=8.80 (s, 3H; H ), 7.65 (s, 3H; H ), 7.65 (d, J=8.5 Hz, 3H;
), 7.47 (d, J=8.5 Hz, 10H; H ), 7.40 (m,
), 7.35 (d, J=8.5 Hz, 10H; H ), 4.47 (q, J=7.1 Hz, 6H;
), 1.48 (t, J=7.1 Hz, 9H; CH ), 1.30 ppm (s, 45H; CH tBu);
C NMR: (126 MHz, CD Cl ): d=166.97, 150.64, 143.18, 141.01, 139.76,
37.17, 134.20, 132.45, 128.82, 126.40, 125.78, 125.70, 125.49, 120.92,
19.81, 113.91, 88.97, 61.29, 34.46, 31.09, 14.33 ppm; UV/Vis (CH Cl ):
max (e)=269 (97000), 343 (26000), 366 nm (22000 mol Lcm ); MS
3
-Acetyl-1,5-dicyano-3-phenylpentane (7): In a two-necked flask, acrylo-
2
Cl
2
d
a
nitrile (33 mL, 0.5 mol, 2 equiv) was added dropwise under vigorous stir-
ring to a solution of phenylacetone (33 mL, 0.25 mol, 1 equiv) and “tri-
tonB” (2.63mL, 0.015 mol) in tert-butanol (64 mL) at a temperature kept
between 20 and 258C. After the end of the addition, the mixture was
stirred for one additional hour. After filtration and washing with metha-
H
c
), 7.55 (d, J=8.5 Hz, 10H; H
3H; H
OCH
1
3
1
4
H
b
2
2
3
3
1
3
2
2
1
1
l
nol, a white solid was obtained. Recrystallisation in ethanol yielded 7 as
1
2
2
a white solid (45.79 g, 76%). H NMR (250 MHz, CD
Cl
): d=7.44–7.37
CN), 2.19–
): m/z: 258
2
2
À1
À1
(
2
m, 3H; Ph), 7.18–7.14 (m, 2H; Ph), 2.43–2.23 (m, 4H; CH
.01 (m, 4H; CH ), 1.94 ppm (s, 3H; Me); MS (DCI/NH
3
2
+
+
(
FAB): m/z: 1787 [M] ; HR LSI: m/z calcd for C115
H
113BN
6
O
6
Ru [M] :
NPF ; vs.
2
+
1
787.7936; found: 1787.7908 (100% [M] ); CV (CH
2
Cl
2
, nBu
4
6
+
[
M+NH
4
] .
À1
SCE; sweep rate: 100 mVs ): ERuII/RuIII : +0.77 V rev.
3
-Acetyl-3-phenyl-1,5-pentanedicarboxylic acid (8): In a round-bottomed
5
h -1,2,3,4,5-Penta-[4-(ferrocenyl)phenyl]cyclopentadienylhydrotris[6-
flask, 7 (45.79 g, 0.190 mol, 1 equiv) was heated at reflux overnight in
water (210 mL) with KOH (21 g, 0.526 mol, 2.75 equiv). Activated char-
coal was added and the mixture was filtered over celite. The filtrate was
acidified with concentred hydrochloric acid to yield a white precipitate.
(
ethoxycarbonyl)indazol-1-yl]borateruthenium(II) (5): In a Schlenk tube,
compound (35 mg, 0.023 mmol, 1 equiv), ferroceneboronic acid
106 mg, 0.46 mmol, 20 equiv), palladium acetate (2.6 mg, 12 mmol,
3
(
0
2
.5 equiv), 2-(2’,6’-dimethoxybiphenyl)dicyclohexylphosphane (9.5 mg,
3 mmol, 1 equiv) and anhydrous K PO (49 mg, 0.23mmol, 10 equiv)
The product was recrystallised in water to give 8 as a white solid (38.50 g,
1
3
4
7
7
2
2%). H NMR: (250 MHz, [D
]acetone): d=7.47–7.40 (m, 2H; Ph),
6
were placed under argon. Freshly distilled toluene (2 mL) was added and
the mixture was heated at 1008C overnight. After cooling down addition-
al ferroceneboronic acid (106 mg, 0.46 mmol, 20 equiv), palladium ace-
tate (2.6 mg, 12 mmol, 0.5 equiv), 2-(2’,6’-dimethoxybiphenyl)dicyclohex-
.36–7.28 (m, 3H; Ph), 2.36–2.28 (m, 4H; CH
H; CH ), 1.89 ppm (s, 3H; Me); MS (DCI/NH
-Acetyl-4-phenylcyclohexanone (9): In
2
COOH), 2.11–2.03(m,
): m/z: 277 [MÀH] .
round-bottomed flask,
À
2
3
4
a
8
(
38.50 g, 0.138 mol, 1 equiv) and potassium acetate (0.38 g, 3.84 mmol,
ylphosphane (9.5 mg, 23 mmol, 1 equiv) and anhydrous K
.23mmol, 10 equiv) were added and the mixture was heated at 100 8C
overnight. The crude reaction mixture was evaporated under vacuum.
The product was purified by column chromatography (SiO : CH Cl ) to
give 5 as an orange solid (15 mg, 32%). H NMR: (500 MHz, CD Cl ):
d=8.80 (s, 3H; H ), 8.25 (s, 3H; H ), 7.64 (d, J=8.5 Hz, 3H; H ), 7.45
d, J=8.5 Hz, 3H; H ), 7.35 (d, J=8.5 Hz, 10H; H ), 7.22 (d, J=8.5 Hz,
0H; H ), 4.55 (t, J=1.8 Hz, 10H; H ), 4.46 (q, J=7.1 Hz, 6H; OCH ),
.25 (t, J=1.8 Hz, 10H; H ), 3.94 (s, 25H; Cp), 1.47 ppm (t, J=7.1 Hz,
); C NMR: (126 MHz, CD Cl ): d=166.95, 143.18, 140.55,
38.63, 133.49, 131.51, 128.75, 125.49, 124.83, 120.98, 119.72, 113.94, 88.55,
4.18, 69.87, 69.30, 66.42, 61.29, 14.32 ppm; UV/Vis (CH Cl ): lmax (e)=
85 (99000), 340 (54000), 362 nm (49000 mol Lcm ); MS (MALDI-
3 4
PO (49 mg,
2
5
.8%) were heated at reflux in acetic anhydride (71 mL, 1.39 mol,
equiv) for 2 h. The acetic acid formed was distilled under reduced pres-
0
sure, and then the mixture was heated at 2508C to distil the cyclohexa-
2
2
2
none. After recrystallisation in hexane 9 was obtained as a white solid
1
2
2
1
(
13.43 g, 45%). H NMR: (250 MHz, CD
2
Cl
2
): d=7.41–7.34 (m, 5H; Ph),
); MS (DCI/NH ): m/z:
d
a
c
2
2
.49–2.32 (m, 8H; CH
2
), 1.97 ppm (s, 3H; CH
3
3
(
b
1
+
+
34 [M+NH
4
] , 251 [M+N
2 7
H ] .
1
4
9
1
8
2
2
3
2
1
-Hydroxy-4-phenylbicyclo
ACHTREUNG
[2.2.2]octan-3-one (10): In a round bottomed
4
1
3
flask, 9 (10.63g, 0.049 mol, 1 equiv) was added to a solution of potassium
hydroxide (11.8 g, 0.211 mol, 4.3equiv) in absolute ethanol (52 mL). The
mixture was stirred at room temperature overnight. Water was added
(150 mL) and the precipitate was filtered and washed with water. After
H; CH
3
2
2
2
2
À1
À1
+
+
drying under vacuum 10 was obtained as a white solid was obtained
TOF): m/z: 2046 [M] ; HR LSI: m/z calcd for C115
H
93BFe
5
N
6
O
6
Ru [M] :
NPF ; vs.
1
+
(7.77 g, 73%). H NMR: (250 MHz, CD
2
Cl
2
): d=7.36–7.16 (m, 5H; Ph),
bicyclo), 1.67 ppm
2
046.3040; found: 2046.3023 (100% [M] ); CV (CH
2
Cl
2
, nBu
4
6
À1
2.56–2.55 (m, 2H; CH
s, 1H; OH); MS (DCI/NH
1-Hydroxy-4-phenylbicyclo[2.2.2]octane (11): In a round-bottomed flask,
0 (7.77 g, 0.036 mol, 1 equiv) was heated at reflux in hydrazine hydrate
2
-CO), 2.27–1.85 (m, 8H; CH
2
SCE, sweep rate 100 mVs ): EFeII/FeIII : +0.47 V rev (5e); ERuII/RuIII : 0.89 V,
+
+
(
3 4 2 7
): m/z: 23 4 [M +NH ] , 251 [M+N H ] .
rev (1e).
5
ACHTREUNG
h –1,2,3,4,5-penta[4-[4-ferrocenylphenyl)-4-phenyl-bicyclo
A
H
R
U
G
1
phenyl] cyclopentadienyl hydrotris[6-(ethoxycarbonyl) indazol-1-yl]bo-
rate ruthenium(II) (6): In Schlenk tube, compound (25 mg,
.016 mmol, 1 equiv), compound 15 (75 mg, 0.13mmol, 8 equiv), palladi-
um acetate (1.8 mg, 8 mmol, 0.5 equiv), 2-(2’,6’-dimethoxybiphenyl)dicy-
clohexylphosphane (6.8 mg, 16 mmol, 1 equiv) and anhydrous PO
35 mg, 0.16 mmol, 10 equiv) were placed under argon. Freshly distilled
(
(
45 mL) for 5 h. After the mixture was cooled, potassium hydroxide
10.1 g, 0.18 mol) and diethyleneglycol (63mL) were added. The appara-
a
3
0
tus was set up for distillation and the temperature was set at 1608C for
h, then the temperature was raised to 2208C and this temperature was
1
K
3
4
maintained until the end of the nitrogen evolution. The reaction mixture
was cooled down and poured into water (300 mL), extracted with diethyl
ether, washed with hydrochloric acid (1m) and dried over magnesium sul-
(
toluene (1.5 mL) and degassed water (100 mL) were added and the mix-
ture was heated at 1008C overnight. After cooling down, additional ester
fate. Crystallisation from cyclohexane gave 11 as a white solid (4.57 g,
1
0
1
5
(75 mg, 0.13mmol, 8 equiv), palladium acetate (1.8 mg, 8 mmol,
.5 equiv), 2-(2’,6’-dimethoxybiphenyl)dicyclohexylphosphane (6.8 mg,
6 mmol, 1 equiv) and anhydrous K PO (35 mg, 0.16 mmol, 10 equiv)
1
6
1
1
2%). H NMR: (250 MHz, CD
2
Cl
2
): d=7.33–7.26 (m, 5H; Ph), 2.00–
bicyclo), 1.43ppm (s,
.94 (m, 6H; CH
H; OH); MS (FAB): m/z: 202 [M] .
,4-Diphenylbicyclo[2.2.2]octane (12): Concentrated sulfuric acid
2
bicyclo), 1.77–1.72 (m, 6H; CH
2
3
4
+
were added and the mixture was heated at 1008C overnight. The crude
reaction mixture was evaporated under vacuum. The product was puri-
1
ACHTREUNG
(
5.3mL) was added under argon to a stirred solution of 11 in a round-
fied by column chromatography (SiO
2
: CH
solid (16 mg, 29%). H NMR: (500 MHz, CD
.20 (s, 3H; H ), 7.66 (d, J=8.5 Hz, 3H; H ), 7.57 (d, J=8.4 Hz, 10H;
), 7.50 (d, J=8.5 Hz, 10H; H ), 7.44–7.37 (m, 33H; H ,H ,H ,H ), 7.28
d, J=8.5 Hz, 10H; H ), 4.60 (t, J=1.8 Hz, 10H; H ), 4.48 (q, J=7.1 Hz,
), 4.28 (t, J=1.8 Hz, 10H; H ), 4.03(s, 25H; Cp), 1.98 (s,
bicyclo), 1.49 ppm (t, J=7.1 Hz, 9H; CH
Cl ): d=166.97, 149.52, 147.68, 143.19, 141.03, 139.74,
2
Cl
2
) to give 6 as an orange
1
bottomed flask, (4.58 g, 0.23mol, 1 equiv) in benzene (5 30 mL). The mix-
ture was heated at reflux for 4 h. After cooling, the mixture was poured
into water (500 mL) and extracted with dichloromethane. Purification by
2
Cl
2
): d=8.81 (s, 3H; H ),
d
8
a
c
H
1
4
2
3
5
b
column chromatography (SiO
white solid (2.0 g, 33%). H NMR: (300 MHz, CD
2
: hexane/CH
2
Cl
2
5%) afforded 12 as a
Cl ): d=7.41–7.37 (m,
(
6
7
1
6
6
H; OCH
0H; CH
2
8
2
2
13
4H; H ), 7.34–7.29 (m, 4H; H ), 7.21–7.16 (m, 2H; H ), 1.98 ppm (s,
); C NMR:
o
m
p
2
3
1
3
1
2H; CH
2
bicyclo); C NMR: (76 MHz, CD
2
Cl
2
): d=150.08, 128.12,
(
126 MHz, CD
2
2
+
1
25.59, 35.04, 32.84 ppm; MS (DCI/NH
[2.2.2]octane (13):
(0.78 mL, 15.2 mol, 2 equiv) in CCl (67 mL) was added to a solution of
12 (2.0 g, 7.6 mmol, 1 equiv) and iron powder (87 mg, 1.56 mmol,
3
): m/z: 262 [M] .
1
1
3
37.31, 136.31, 134.22, 132.48, 128.84, 126.46, 126.07, 125.97, 125.72,
25.50, 120.94, 119.83, 113.91, 88.99, 85.70, 68.52, 68.76, 66.48, 61.30,
1,4-Di-(4-bromophenyl)bicyclo
A
H
R
U
G
A solution of Br
2
4.92, 34.83, 32.83, 32.77, 14.34; UV/Vis (CH
2
Cl
2
):
l
max (e)=277
4
À1
À1
(
205000), 342 (44000), 368 nm (31000 mol Lcm ); MS (MALDI-
Chem. Eur. J. 2007, 13, 5622 – 5631
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5629