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M. Berthod et al. / Tetrahedron: Asymmetry 15 (2004) 1121–1126
7.6–7.7 (m, 4H), 7.75 (s, 2H), 8.23 (d, 2H, J ¼ 8:4). 13C
NMR (75 MHz, CDCl3): 123.3, 123.5, 127.1, 127.5,
127.8, 128.3, 128.5, 128.7, 129.0, 130.3, 131.6, 131.7,
131.8, 131.8, 131.9, 131.9, 132.3, 132.4, 132.7, 132.8,
132.9, 133.0, 133.1, 133.3, 134.4, 134.7, 134.9, 142.2,
6.87 (m, 4H), 7.22–7.55 (m, 20H), 7.68–7.79 (m, 4H),
8.25 (d, 2H, J ¼ 9). 13C NMR (75 MHz, CDCl3): 113.8,
115.8, 119.5, 125.0, 126.7, 126.9, 127.7, 128.1, 128.4,
128.6, 128.7, 128.9, 129.3, 130.2, 130.3, 130.9, 131.2,
131.7, 131.8, 132.1, 132.3, 132.6, 132.7, 132.8, 132.9,
134.1, 147.7, 150.4. 31P NMR (81 MHz, CDCl3): 29.07.
19F NMR (282 MHz, CDCl3): )126.60 (s, 4F), )123.16
(s, 4F), )122.17 (d, 16F, J ¼ 53:8), )121.64 (s, 4F),
142.3, 142.4. 31P NMR (81 MHz, CDCl3): 27,60.
25
D
½a ¼ ꢀ96:4 for (S) (c 1, DMF). ESIþ: MHþ ¼ 813:33.
Mp: >300 ꢁC. Calcd C 65.05, H 3.72, O 3.94, P 7.62, Br
19.67; found C 65.13, H 3.82, O 3.73, P 7.81, Br 19.42.
)120.57 (s, 4F), )105.2 (s, 4F), )81.14 (s, 6H).
25
½a ¼ þ31:3 (c 2.3, DMF). ESIþ: MHþ ¼ 1691:36. Mp:
D
4.4. (R)-5,50-DibromoBINAPO 211
>300 ꢁC. Calcd C 45.46, H 1.79, F 47.19; found C 44.93,
H 1.83, F 47.13.
The compound was synthesized as described in the Ref.
11. 1H NMR (200 MHz, CDCl3): 6.62 (t, 2H, J ¼ 15:0),
6.72 (d, 2H, J ¼ 9:0), 7.2–7.5 (m, 20H), 7.55 (dd, 2H,
J ¼ 3:0, 1.0), 7.6–7.8 (m, 2H), 8.3 (dd, 2H, J ¼ 1:7, 9.0).
13C NMR (75 MHz, CDCl3): 123.2, 126.5, 127.1, 127.3,
128.5, 128.7, 129.9, 131.6, 131.8, 132.1, 132.3, 132.5,
4.8. (R)-5,50-PerfluorohexylBINAPO 5
The compound was synthesized as described in the
1
typical procedure. H NMR (300 MHz, CDCl3): 6.73–
6.91 (m, 4H), 7.17–7.41 (m, 18H), 7.51 (dd, 2H, J ¼ 9:4,
11.7), 7.63–7.72 (m, 4H), 8.27 (d, 2H, J ¼ 8:3). 13C
NMR (75 MHz, CDCl3): 116.3, 120.2, 124.5, 124.8,
125.3, 126.5, 128.4, 128.5, 128.6, 128.7, 128.9, 129.4,
129.7, 130.1, 130.3, 130.4, 131.1, 131.4, 131.6, 132.1,
132.2, 132.3, 132.7, 132.8, 133.1. 31P NMR (81 MHz,
CDCl3): 28.33. 19F NMR (282 MHz, CDCl3): )126.37
132.8, 132.9, 133.4, 135.0. 31P NMR (81 MHz, CDCl3):
25
29.20. ½a ¼ þ97:7 for (R) (c 1, DMF). ESIþ:
D
MHþ ¼ 813:32. Mp: >300 ꢁC. Calcd C 65.05, H 3.72, O
3.94, P 7.62, Br 19.67; found C 65.34, H 4.05, O 3.41, P
7.46, Br 19.44.
4.5. Typical procedure for the (R)- or (S)-perfluoro-
alkylBINAPO
(s, 4F), )123.01 (s, 4F), )121.79 (s, 4F), )120.64 (s, 4F),
25
D
)105.21 (s, 4F), )þ81.15 (s, 6H). ½a ¼ þ72:1 (c 1,
DMF). ESIþ: MH ¼ 1291:24. Mp: >300 ꢁC. Calcd C
A mixture of (R)- or (S)-4,40- or 5,50-dibromoBINAPO
(2.46 mmol, 1 equiv), perfluoroalkyliodide (7.38 mmol,
3 equiv), copper powder (14.76 mmol, 6 equiv), 2,20-bi-
pyridine (0.5 mmol, 0.2 equiv), C6H5F (20 mL) and
DMSO (20 mL) was stirred for 3 days at 80 ꢁC. After
cooling to room temperature, the reaction mixture was
diluted with water (40 mL) and DCM (50 mL) and then
filtered. The organic layer was separated and washed
with water (20 mL), a solution of hydrochloric acid
(0.1 M, 30 mL), a solution of sodium bicarbonate
(30 mL), dried over MgSO4 and evaporated under
reduced pressure. The resulting solid was crystallized in
toluene to give a white solid (2.34 mmol, 95%).
52.11, H 2.34, F 38.27; found C 52.02, H 2.47, F 38.45.
4.9. (R)-5,50-PerfluorooctylBINAPO 6
The compound was synthesized as described in the
1
typical procedure. H NMR (300 MHz, CDCl3): 6.75–
6.96 (m, 4H), 7.19–7.40 (m, 18H), 7.56 (dd, 2H, J ¼ 9:4,
11.7), 7.65–7.73 (m, 4H), 8.28 (d, 2H, J ¼ 8:6). 13C
NMR (75 MHz, CDCl3): 124.5, 124.9, 125.2, 126.7,
128.4, 128.5, 128.6, 128.7, 128.8, 129.3, 129.7, 130.1,
130.2, 130.4, 130.9, 131.5, 131.6, 132.0, 132.2, 132.3,
132.7, 132.8, 132.9. 31P NMR (81 MHz, CDCl3): 28.58.
19F NMR (282 MHz, CDCl3): )126.54 (s, 4F), )123.09
4.6. (R)-4,40-PerfluorohexylBINAPO 3
(s, 4F), )122.26 (s, 8F), )121.64 (s, 4F), )120.19 (s, 4F),
25
D
)104.35 (s, 4F), )þ81.18 (s, 6F). ½a ¼ þ73:4 (c 1,
DMF). ESIþ: MH ¼ 1491:54. Mp: >300 ꢁC. Calcd C
The compound was synthesized as described in the
1
typical procedure. H NMR (200 MHz, CDCl3): 6.76–
48.34, H 2.03, F 43.33; found C 48.91, H 1.88, F 43.67.
6.86 (m, 4H), 7.22–7.50 (m, 20H), 7.67–7.77 (m, 4H),
8.24 (d, 2H, J ¼ 8:6). 13C NMR (75 MHz, CDCl3):
115.8, 119.4, 125.1, 126.8, 127.1, 127.4, 127.7, 128.1,
128.4, 128.4, 128.6, 128.7, 128.8, 128.9, 129.2, 129.3,
130.5, 131.0, 131.8, 132.1, 132.3, 132.8, 132.9, 150.4. 31P
NMR (81 MHz, CDCl3): 28.93. 19F NMR (282 MHz,
CDCl3): )126.38 (s, 4F), )122.98 (s, 4F), )121.78
4.10. Typical procedure for the (R)- or (S)-perfluoro-
alkylBINAP (reduction procedure)
In a 25 mL round-bottomed flask under an inert atmo-
sphere in a reflux condenser was placed (R)- or (S)-4,40-
or 5,50-perfluoroalkylBINAPO (0.6 mmol, 1 equiv).
Degassed phenylsilane (8 mL) added. The mixture was
heated to 130 ꢁC and trichlorosilane was added in three
portions (3 · 1 mL) after 1, 3 and 15 h. After the last
addition the solution was stirred for 2 h, cooled and
evaporated till a white solid was obtained. This was
washed with cyclohexane, filtered on Millipore and
evaporated. The resulting solid was dissolved in DCM,
filtered on a thin pad of silica gel and evaporated to give
a white crystalline solid in 95% yield.
(s, 4F), )120.62 (s, 4F), )105.21 (m, 4F), )81.14 (s, 6H).
25
½a ¼ þ33:2 (c 2.3, DMF). ESIþ: MHþ ¼ 1291:43. Mp:
D
>300 ꢁC. Calcd C 52.11, H 2.34, F 38.27; found C 51.57,
H 2.56, F 38.13.
4.7. (R)-4,40-perfluorodecylBINAPO 4
The compound was synthesized as described in the
1
typical procedure. H NMR (300 MHz, CDCl3): 6.77–