C. J. Diez-Holz, C. Böing, G. Franciò, M. Hölscher, W. Leitner
FULL PAPER
(
1.76 g, 3.17 mmol) was separated by column chromatography un-
Experimental Section
der inert gas conditions (Silicagel 60, 0.040–0.063 µm, THF/n-pen-
tane, 1:10) and led to the isolation of (R ,R )-6 (476 mg, 0.86 mmol,
7%) and (R ,S )-6 (370 mg, 0.67 mmol, 21%). (R
600 MHz, CDCl
General: All reactions were carried out under an atmosphere of dry
and oxygen-free argon with the use of standard Schlenk techniques.
All solvents were dried and distilled prior to use. NMR spectra
were measured at room temperature with a Bruker AV-600 spec-
a
c
1
2
(
a
c
a
,R
c
)-6: H NMR
3
4
3
): δ = 5.23 (dd, J = 6.4, J = 2.5 Hz, 1 H), 6.23
3
3
3
(dd, J = 9.3 Hz, J = 6.4 Hz, 1 H), 6.46 (d, J = 9.3 Hz, 1 H),
trometer. Chemical shifts are given relative to TMS by using the
3
3
7
1
1
8
.01–7.06 (m, 3 H), 7.08 (t, J = 7.5 Hz, 1 H), 7.11 (d, J = 8.7 Hz,
solvent signals as internal reference for 1H NMR as well as
13
C
3
H), 7.24–7.29 (m, 3 H), 7.30–7.41 (m, 4 H), 7.44 (d, J = 8.1 Hz,
H), 7.48–7.52 (m, 3 H), 7.57 (d, J = 8.7 Hz, 1 H), 7.84 (d, J =
.1 Hz, 1 H), 7.99 (d, J = 8.1 Hz, 1 H), 8.04 (d, J = 8.7 Hz, 1 H)
NMR and H
3
PO
4
(85%) as external reference for 31P NMR spec-
3
3
1
troscopy. H NOESY measurements were carried out by using a
3
3
mixing time of 500 ms. 1-Naphthyllithium,[25] (R)-3,5-dioxa-4-
13
1
ppm. C{ H} NMR (150 MHz, CDCl
3
): δ = 52.6, 122.1, 122.2,
phosphacyclohepta[2,1-a;3,4-aЈ]dinaphthalene [(R)-3],[
12]
[{Ni-
1
1
1
22.3, 123.8, 124.3, 124.8, 124.9, 125.2, 125.6, 125.8, 126.1, 126.4,
[
26]
[27]
(
allyl)Br}
2
]
and [Ni(allyl)(cod)][SbF
6
]
were prepared accord-
26.9, 127.2, 127.3, 128.3, 128.5, 129.6, 130.7, 131.0, 131.2, 131.2,
31.7, 131.8, 132.5, 133.0, 136.1, 136.2, 141.8, 149.0, 149.1 ppm.
ing literature procedures. 8-Chloroquinoline was purchased from
TCI and distilled prior to use. All other reagents were ordered from
Sigma–Aldrich. Styrene was distilled and diethyl diallylmalonate
degassed by three freeze–pump–thaw cycles prior to use. Alkyllith-
ium reagents were titrated with N-benzylbenzamide.[ All other
reagents were used as purchased.
31
1
1
P{ H} NMR (242 MHz, CDCl
3 a c
): δ = 143.2 ppm. (R ,S )-6: H
3
4
NMR (600 MHz, CDCl ): δ = 5.01 (dd, J = 5.8 Hz, J = 2.5 Hz,
3
3
3
3
1
1
7
8
H), 6.08 (dd, J = 9.5 Hz, J = 5.8 Hz, 1 H), 6.81 (d, J = 9.5 Hz,
28]
3
3
H), 6.99 (d, J = 7.7 Hz, 1 H), 7.05–7.08 (m, 2 H), 7.12 (t, J =
3
.6 Hz, 1 H), 7.22–7.31 (m, 2 H), 7.39–7.46 (m, 4 H), 7.48 (d, J =
.7 Hz, 1 H), 7.73 (d, J = 8.8 Hz, 1 H), 7.92–7.98 (m, 4 H), 8.05
3
2
-Methyl-8-chloro-1-(3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-aЈ]-
3
13
1
(
d, J = 8.8 Hz, 1 H) ppm. C{ H} NMR (150 MHz, CDCl
3
): δ
dinaphthalen-4-yl)-1,2-dihydroquinoline (5): Methyllithium (1.48
in diethyl ether, 2.9 mL, 4.2 mmol) was added dropwise at –78 °C
to a solution of 8-chloroquinoline (0.5 mL, 3.9 mmol) in THF
=
52.2, 122.4, 122.5, 123.6, 125.0, 125.1, 125.2, 125.3, 125.6, 126.3,
26.4, 127.3, 127.3, 127.4, 127.4, 127.9, 128.1, 128.4, 128.6, 129.2,
1
1
1
1
5
29.6, 129.9, 130.9, 131.0, 131.1, 131.5, 131.9, 132.0, 132.1, 135.9,
(10 mL). The reaction mixture was then warmed to –50 °C, stirred
3
1
1
39.8, 148.6, 149.2 ppm. P{ H} NMR (242 MHz, CDCl
3
): δ =
for 1 h and cooled down again to –78 °C. The resulting orange
solution was added at –78 °C to a solution of (R)-3,5-dioxa-4-phos-
phacyclohepta[2,1-a;3,4-aЈ]dinaphthalene [(R)-3, 1.36 g, 3.9 mmol]
in THF (3.0 mL). The reaction mixture was slowly warmed to
room temp. and stirred for an additional 2 h. The solvent was evap-
orated, and the crude brown residue was suspended in toluene
33.9 ppm. HRMS (ESI+): calcd. for C35
78.105079; found 578.104713.
H
23ClNNaO
2
P
2
-(1-Naphthalene)-8-chloro-1-(3,5-dioxa-4-phosphacyclohepta[2,1-
a;3,4-aЈ]dinaphthalen-4-yl)-1,2-dihydroquinoline (7): 8-Chloroquino-
line (0.8 mL, 6.2 mmol) was rapidly added at room temp. to a solu-
tion of 1-naphthyllithium (0.33 in THF, 19.6 mL, 6.2 mmol). The
resulting dark brown solution was stirred for 1 h before it was
added to a solution of (R)-3,5-dioxa-4-phosphacyclohepta[2,1-
a;3,4-aЈ]dinaphthalene [(R)-3, 2.17 g, 6.2 mmol] in THF (7.0 mL).
After 2 h, the solvent was evaporated and the crude brown residue
was suspended in toluene (15.0 mL) and filtered through a pad of
celite. After evaporation of the solvent, the title compound was
obtained as a yellow solid as a 1:1 diastereomeric mixture. The two
diastereoisomers were separated by extraction with dichlorometh-
ane (15.0 mL). The compound insoluble in dichloromethane
(12 mL) and filtered through a pad of celite. After evaporation of
the solvent, the title compound was obtained as a yellow solid as
a 1:1 diastereomeric mixture. This mixture was recrystallised from
dichloromethane/EtOH. A white solid consisting of pure (R
370 mg, 0.75 mmol, 32%) was obtained. The filtrate was evapo-
rated to dryness, which resulted in a yellow solid (718 mg) that
contained (R ,R )-5 contaminated with 10% of (R ,S )-5. (R ,S )-
: H NMR (600 MHz, CDCl ): δ = 0.82 (d, J = 6. 8 Hz, 3 H),
a c
,S )-5
(
a
c
a
c
a
c
1
3
5
3
3
3
3
3
.94 (m, 1 H), 5.85 (dd, J = 9.4 Hz, J = 5.9 Hz, 1 H), 6.35 (d, J
=
9.4 Hz, 1 H), 7.00 (m, 1 H), 7.02 (m, 1 H), 7.25 (m, 1 H), 7.33
3
3
(
8
7
m, 3 H), 7.44 (m, 4 H), 7.68 (d, J = 8.8 Hz, 1 H), 7.90 (d, J =
a c
proved to be the (R ,S ) diastereoisomer and was obtained as a
3
3
.2 Hz, 1 H), 7.93 (d, J = 8.8 Hz, 1 H), 7.96 (d, J = 8.2 Hz, 1 H),
white solid (638 mg, 1.00 mmol, 37%). The filtrate was evaporated
to dryness and a portion of the resulting solid (1.20 g, ≈70% de-
sired product) was purified by column chromatography under inert
gas conditions (Silicagel 60, 0.040–0.063 µm, dichloromethane/n-
pentane, 1:5) to afford (R
0
(
(
7
H), 7.33 (m, 2 H), 7.41 (m, 3 H), 7.49 (d, J = 8.9 Hz, 1 H), 7.57
(m, 3 H), 7.66 (d, J = 8.7 Hz, 1 H), 7.89 (d, J = 8.2 Hz, 1 H),
7.93 (d, J = 8.8 Hz, 1 H), 8.10 (d, J = 8.1 Hz, 1 H), 8.16 (d, J =
8.7 Hz, 1 H) ppm. C{ H} NMR (150 MHz, CDCl ): δ = 50.9,
3
53.5, 122.0, 122.1, 122.2, 122.7, 123.3, 123.4, 123.8, 124.9, 125.0,
125.1, 125.5, 125.7, 125.8, 126.3, 126.5, 126.9, 127.3, 127.7, 127.9,
128.2, 128.4, 128.5, 129.4, 130.3, 130.6, 130.8, 130.9, 131.6, 131.7,
132.7, 133.1, 133.4, 134.8, 134.9, 137.6, 148.9, 149.9 ppm. P{ H}
NMR (242 MHz, CDCl ): δ = 139.1 ppm. MS (CI): m/z (%) = 607
(1) [M] , 334 (6), 332 (12), 330 (7), 297 (5), 294 (14), 293 (36), 292
(94), 291 (82), 290 (100), 289 (27), 288 (11), 257 (14), 256 (77), 255
(49), 254 (15), 185 (24), 184 (6), 168 (17), 157 (29), 145 (12), 129
3
13
1
3
.99 (d, J = 8.7 Hz, 1 H) ppm. C{ H} NMR (150 MHz, CDCl ):
δ = 18.9, 46.3, 122.2, 122.5, 122.8, 123.4, 124.0, 124.1, 124.8, 125.0,
1
1
1
25.1, 126.3, 126.4, 127.2, 127.3, 128.1, 128.2, 128.6, 128.7, 129.4,
30.0, 130.7, 131.2, 131.4, 131.7, 132.8, 133.0, 134.5, 135.2,
,R
c
)-7 as a white solid (175 mg,
)-7: H NMR (600 MHz, CDCl ): δ = 5.82
t, J = 4.5 Hz, 1 H), 5.94 (dd, J = 9.6 Hz, J = 5.6 Hz, 1 H), 6.37
49.5 ppm. 31P{ H} NMR (242 MHz, CDCl
1
): δ = 144.6 ppm. MS
a
3
1
.29 mmol, 33%). (R
a
,S
c
3
+
(CI): m/z (%) = 496 (9), 495 (8) [M] , 460 (5), 361 (16), 344 (10),
3
3
3
3
1
43 (38), 333 (7), 329 (8), 288 (20), 287 (100), 286 (13), 182 (12),
81 (5), 180 (27), 178 (20), 139 (5). HRMS (EI): calcd. for
3
3
d, J = 8.6 Hz, 1 H), 6.45 (m, 1 H), 6.53 (d, J = 9.6 Hz, 1 H),
3
.06 (m, 2 H), 7.12 (t, J = 7.4 Hz, 1 H), 7.20 (m, 2 H), 7.25 (m, 1
C
30
H21ClNO
2
P 493.09985; found 493.10020.
3
3
3
2
-Phenyl-8-chloro-1-(3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-aЈ]-
3
3
3
dinaphthalen-4-yl)-1,2-dihydroquinoline (6): Phenyllithium (1.5 in
diethyl ether, 5.3 mL, 8.0 mmol) was added dropwise at –78 °C to
a solution of 8-chloroquinoline (1.02 mL, 8.00 mmol) in THF
1
3
1
(
30.0 mL). The resulting solution was added at –78 °C to a solution
of (R)-3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-aЈ]dinaphthalene
(R)-3, 2.79 g, 8.00 mmol] in THF (20 mL). The reaction mixture
3
1
1
[
was stirred for 1 h at –78 °C and for 1 h at room temp. The solvent
was evaporated, and the crude brown residue was suspended in
toluene (20 mL) and filtered through a pad of celite. After evapora-
tion of the solvent, the title compound was obtained as a yellow
solid as a 1:1 diastereomeric mixture. The diastereomeric mixture
3
+
1
(16), 128 (8). (R
a
,R
c
)-7: H NMR (600 MHz, CDCl
3
): δ = 6.08 (dd,
3000
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Eur. J. Org. Chem. 2007, 2995–3002