8
10
M. V. Esc a´ rcega-Bobadilla et al.
with a Hewlett-Packard 5890A instrument in a CHIRAL-
DEX G-TA (30 m 9 025 mm) or Permabond L-Chirasil-
Val column (25 m 9 0.25 mm), equipped with a Hewlett-
Packard HP3396 series II integrator. Catalytic experiments
room temperature overnight. The resulting mixture was fil-
tered through basic alumina under nitrogen atmosphere and
the solvent was evaporated. The final product was obtained
D
as white powder (0.864 g, 60%). a =?22.920 (c = 1.06,
2
5
1
in scCO were performed in a Parr autoclave (25 mL) with
2
CH Cl ). H NMR (400 MHz, CDCl ) d = 3.83 (m, 1H,
2
2
3
1
CHH), 4.23 (m, 1H, CHH), 7.2–8.0 (m, 12H, ar); C NMR
3
magnetic stirring. The autoclave was equipped with a liquid
1
inlet, a gas inlet, a CO inlet and a thermocouple. An
2
(100 MHz, CDCl ) d = 60.7 (q, J = 35 Hz, CH CF ),
3
C-F
2
3
1
111.6 (Cipsoar), 117.6 (CH ), 124.1 (CH ), 124.2 (q, J
electric heating mantle kept the temperature constant. Cat-
alytic experiments with CH Cl , [BMI][PF ] and SILPs
=
C-F
ar
ar
277 Hz, CF ), 124.3 (CH ), 127.5 (CH ), 128.4 (CH ),
ar
2
2
6
3
ar
ar
were performed in a Fisher Porter bottle with magnetic
stirring.
129.5 (C
1
), 131.3 (CH ), 133.6 (C
ar
), 152.3 (Cipsoar);.
ipsoar
31
ipsoar
9
F NMR (376.5 MHz, CDCl ) d = -75.59; P NMR
3
-
1
(162 MHz, CDCl ) d = 136.30. m
(KBr, pellet)/cm
max
3
2
.2 Synthesis of (11bR)-4-(3,5-bis
1215 (C–F, st, w), 977 (P–O–Cal, st, w), 823 (P–C, st, w), 743
(
[
trifluoromethyl)phenoxy)dinaphtho
0
(CF , st, w); elemental analysis calcd (%) for C H F O P:
3 22 14 3 3
0
2,1-d:1 ,2 f][1–3] dioxaphosphepine, 1
C 63.78, H 3.41; found C 63.81, H 3.44.
(R)-BINOL (1 g, 3.5 mmol) was azeotropically dried with
toluene and dissolved in THF (20 mL) and triethylamine
2.4 Synthesis of Rhodium(I) cyclooctadiene-bis-
(11bR)-4-(2,2,2-trifluoroethoxy)-dinaphtho
0
0
(
1 mL). The reaction mixture was cooled at 0 °C and then
[2,1-d:1 ,2 -f][1–3]dioxaphosphepine)
PCl (0.4 mL, 4.6 mmol) were drop wise added and stirred
hexafluorophosphate, Rh1
3
for 6 h at room temperature. Then (3,5-tris(trifluoro-
methyl)phenol (0.5 mL, 3.5 mmol) in THF (10 mL) and
triethylamine (1 mL) were drop wise added at 0 °C over
[Rh(COD) ]PF (30 mg, 0.065 mmol) and 1 (74 mg,
2
6
0.14 mmol) were dissolved in CH Cl (5 mL) and stirred for
2
2
1
5 min and then, the reaction mixture was stirred at room
3 h. Then the solvent was evaporated and the orange solid
1
washed with pentane. (97 mg 92%) H NMR (300 MHz,
temperature overnight. The resulting mixture was filtered
through basic alumina under nitrogen atmosphere and the
solvent was evaporated. The final product was obtained as
CDCl ) d = 1.33 (bs, CH2COD, 1H), 1.75 (bs, CH2COD, 1H),
3
2.05 (bs, CH2COD, 1H), 2.23 (bs, CH2COD, 2H), 2.45 (bs,
D
white powder (0.750 g, 52%). a = ?37.130 (c = 1.02,
CH2COD, 1H), 2.56 (bs, CH2COD, 2H), 4.48 (bs, CHCOD, 2H),
13
2
5
1
CH Cl ). H NMR (400 MHz, CDCl ) d = 6.53–8.05
5.88 (bs, CHCOD, 2H), 6.75–8.24 (CH , 30H); C NMR
2
2
3
ar
1
3
(
15H, ar); C NMR (75 MHz, CDCl ) d = 111.9 (Cipsoar),
(75.47 MHz, CDCl ) d = 28.6 (CH2COD), 29.7 (CH2COD),
3
3
1
14.4 (CH ), 115.8 (CH ), 117.5 (CH ), 121.3 (Cipsoar),
ar
29.9 (CH2COD), 105.5 (CHCOD), 107.4 (CHCOD), 107.5
ar
ar
1
23.1 (q, JC-F = 271 Hz, CF ), 124.3 (CH ), 124.4
1
(CHCOD), 111.4 (CHCOD), 117.8 (CH ),120.2 (CH ), 120.6
ar
3
ar
ar
(
CH ), 127.7 (CH ), 128.5 (CH ), 129.7 (Cipsoar), 131.5
ar
(CH ), 121.5 (CF ), 122 (CF ), 122.7 (Cipsoar), 124 (CHar),
ar 3 3
ar
ar
(
CH ), 133.0 (q, CipsoCF , J = 33 Hz), 133.6 (Cipsoar),
ar
124.3 (CH ), 125.9 (CH ), 126.4 (CH ), 126.7 (CH ), 127
ar ar ar ar
3
C-F
1
52.0 (Cipsoar), 156.3 (Cipsoar) F NMR (376.5 MHz,
9
1
(CH ), 127.5 (CH ), 128.3 (CH ), 128.4 (CH ), 128.7
ar
ar
ar
ar
3
1
CDCl ) d = -63.64;
d = 145.18. mmax (KBr, pellet)/cm 1215 (C–F, st, w),
P NMR (162 MHz, CDCl )
3
(CH ), 129.5 (C
ar
), 131.2 (CH ), 131.4 (CH ), 131.8
ipsoar ar ar
3
-
1
(Cipsoar), 132.2 (Cipsoar), 133.4 (Cipsoar), 134 (Cipsoar), 152.8
1
9
1
151 (P–O–Car, st,w), 948 (P–O, st, w), 786 (P–C, st, w),
(Cipsoar); F NMR (282.4 MHz, CDCl ) d = -62.92 CF ,
3
3
3
1
1
7
46 (C–F, st, w); elemental analysis calcd (%) for
P NMR (121.5 MHz, CDCl ) d = 134.8 (d, JP-Rh
321 Hz). mmax (KBr, pellet)/cm 1213 (C–F, st, w), 816
P–C, st, w), 748 (P–O–Car, st, w), 726 (CF , st, w); ele-
3
-
1
C H F O P: C 61.78, H 2.78; found C 61.90, H 2.83.
28 15 6 3
(
3
2
.3 Synthesis of (11bR)-4-(2,2,2-
mental analysis calcd (%) for C H F O P : C 57.28, H
64 42 18 6 3
0
0
trifluoroethoxy)dinaphtho[2,1-d:1 ,2 -f][1–3]
3.15; found C57.54, H 3.13. .
dioxa-phosphepine, 2
2
.5 Synthesis of Rhodium(I) cycloctadiene-bis-
((3aS,6aS)-5-benzyl-2-phenyltetrahydro-3aH-
[1–3]dioxaphospholo[4,5-c]pyrrole)
hexafluorophosphate, Rh3
(R)-BINOL (1 g, 3.5 mmol) was azeotropically dried with
toluene and dissolved in THF (20 mL) and triethylamine
(
1 mL). The reaction mixture was cooled at 0 °C and then
PCl (0.4 mL, 4.6 mmol) were drop wise added and stirred
3
for 6 h at room temperature. Then (2,2,2-trifluoroethanol
[Rh(COD) ]PF (15 mg, 0.033 mmol) and 3 (41 mg,
2 6
(
(
0.6 mL, 3.5 mmol) in THF (10 mL) and triethylamine
0.14 mmol) were dissolved in CH Cl (5 mL) and stirred
2 2
1 mL) were drop wise added at 0 °C over a period of time
for 3 h. Then the solvent was evaporated and the yellow
1
solid washed with pentane. (31 mg 87%) H NMR
of 15 min and then, the reaction mixture was stirred at
1
23