A. Oukhrib et al. / Tetrahedron 70 (2014) 1431e1436
1435
132.8, 131.2, 130.6, 130.4 (d, J¼22.7 Hz), 129.6 (d, J¼1.0 Hz),
128.9e128.6 (m, 4C), 127.9 (d, J¼4.4 Hz), 127.8 (d, J¼3.9 Hz), 126.3.
MS(EI): m/z(%)¼294.1 (68) [Mþ], 259 (100) [MþꢀCl], 181.1 (38)
[MþꢀClꢀPh]. HRMS for C18H12ClNaOP: calcd 333.0207; found
333.0184.
152 (11) [Mþꢀ2 Ph]. HRMS for C19H13NaO2P: calcd 327.0545; found
327.0574.
4.2.10. 2,2-Difluoro-6-phenyl-6H-benzo[2,3]phosphindolo[4,5-d][1,3]
dioxole (4b). Yellow oil (30%). 31P NMR (CDCl3, 161 MHz):
d
(ppm)¼ꢀ4.53. 1H NMR (300 MHz, CDCl3):
d
(ppm)¼8.05 (d,
4.2.5. 1-Bromo-5-phenyl-5H-dibenzophosphole (3f). Colorless solid
J¼7.7 Hz, 1H), 7.7e7.6 (m, 1H), 7.5 (td, J¼7.5, 1.2 Hz, 1H), 7.4e7.3 (m,
(37%). Mp 115e116 ꢁC. 31P NMR (CDCl3,161 MHz):
d
(ppm)¼ꢀ9.3. 1H
2H), 7.3e7.1 (m, 5H), 7.00 (dd, J¼8.0, 2.2 Hz, 1H). 13C NMR (75 MHz,
NMR (CDCl3, 300 MHz):
d
(ppm)¼9.12 (d, J¼8.2 Hz, 1H), 7.8e7.6 (m,
CDCl3):
d
(ppm)¼144.3, 143.3 (d, J¼4.8 Hz), 139.6, 138.5 (d,
3H), 7.55 (td, J¼7.8, 1.2 Hz, 1H), 7.41 (td, J¼7.3, 1.7 Hz, 1H), 7.3e7.2
J¼5.3 Hz), 135.8 (d, J¼19.7 Hz), 132.5, 132.0 (t, J¼256 Hz), 130.3
(d, J¼21.9 Hz), 129.7, 129.2, 128.9e128.8 (m, 3C), 128.4e128.3
(m, 1C), 128.2 (d, J¼25.0 Hz), 125.5 (d, J¼24.1 Hz), 125.1, 123.9,
123.1, 108.5e108.3 (m, 1C). MS(EI): m/z(%)¼340.1 (100) [Mþ],
308.2 (15) [MþꢀFꢀO], 273.2 (21) [MþꢀOCF2], 263.1 (34) [MþꢀPh],
234.2 (47) [MþꢀPPh],169.1 (64) [MþꢀPPhꢀOCF2], 139.2 (80)
[MþꢀPPhꢀPhꢀF].
(m, 5H), 7.15 (td, J¼7.6, 2.5 Hz, 1H). 13C NMR (75 MHz, CDCl3):
d
(ppm)¼146.7 (d, J¼3.8 Hz), 143.3 (d, J¼3.4 Hz, 2C), 140.7 (d,
J¼2.4 Hz), 135.9 (d, J¼19.9 Hz), 134.9, 132.9 (d, J¼20.4 Hz, 2C), 130.4
(d, J¼22.7 Hz), 129.7, 129.6 (d, J¼23.1 Hz), 128.8 (d, J¼7.7 Hz, 2C),
128.3, 128.0 (m, 2C), 126.0, 118.7. MS(EI): m/z(%)¼340.1 (38) [Mþ],
259.2 (100) [MþꢀBr], 181.1 (31) [MþꢀBrꢀPh]. HRMS for
C
18H12BrNaP: calcd 360.9752; found 360.9753.
4.2.11. 2,2,3,3-Tetrafluoro-7-phenyl-3,7-dihydro-2H-benzo[2,3]phos-
phindolo[4,5-b][1,4]dioxine (4c). Orange solid (45%). Mp 84e85 ꢁC.
4.2.6. 1,5-Diphenyl-5H-dibenzophosphole (3g). Colorless oil (63%).
31P NMR (161 MHz, CDCl3):
d
(ppm)¼ꢀ10.5. 1H NMR (300 MHz,
31P NMR (CDCl3, 161 MHz):
d
(ppm)¼ꢀ7.11. 1H NMR (300 MHz,
CDCl3):
d
(ppm)¼7.7e7.6 (m, 2H), 7.5e7.3 (m, 5H), 7.3e7.1 (m, 11H),
CDCl3):
d
(ppm)¼8.34 (d, J¼7.9 Hz), 7.36 (t, J¼6.7 Hz), 7.46 (td, J¼7.6,
7.00 (td, J¼8.3, 1.4 Hz, 2H), 6.85 (d, J¼8.0 Hz, 2H). 13C NMR (75 MHz,
1.2 Hz), 7.4e7.3 (m, 2H), 7.3e7.1 (m, 6H), 7.03 (dd, J¼8.2, 2.3 Hz, 1H).
CDCl3):
d
(ppm)¼144.0 (d, J¼2.7 Hz), 143.9 (d, J¼1.6 Hz), 143.2,
13C NMR (75 MHz, CDCl3):
d
(ppm)¼143.5 (d, J¼2.9 Hz), 141.0 (d,
142.0, 140.4 (d, J¼2.7 Hz), 139.6, 136.6 (d, J¼20.1 Hz), 132.9 (d,
J¼20.1 Hz, 2C),131.4,130.4 (d, J¼22.4 Hz),129.6 (d, J¼22.9),129.3 (d,
J¼5.0 Hz, 2C), 128.9e128.6 (m, 5C), 128.0, 127.6, 127.0 (d, J¼8.0 Hz),
126.7 (d, J¼8.6 Hz), 125.4. MS(EI): m/z(%)¼336.2 (100) [Mþ], 257.1
(89) [MþꢀPh], 226.1 (21) [MþꢀPhꢀP]. HRMS for C24H17NaP: calcd
359.0960; found 359.0969.
J¼4.4 Hz),140.8 (d, J¼1.1 Hz),138.1,135.1 (d, J¼19.4 Hz),134.5,133.0,
132.8, 132.5 (d, J¼4.3 Hz), 130.4 (d, J¼22.3 Hz), 129.9, 129.3, 129.2,
129.0, 128.3 (d, J¼8.1 Hz), 126.8 (d, J¼23.4 Hz), 126.4, 116.6 (d,
J¼8.5 Hz), 112.5 (ttd, J¼269.3, 81.0, 16.0 Hz, 2C). MS(EI): m/z(%)¼
390.1 (100) [Mþ], 359.2 (29) [MþꢀOꢀF], 313.1 (67) [MþꢀPh], 295.2
(14) [MþꢀPhꢀF], 202.2 (12) [MþꢀPPhꢀCF2ꢀOꢀF], 169.1 (24)
[MþꢀPPhꢀPhꢀ2 F], 157.1 (44) [MþꢀPPhꢀPhꢀCF2].
4.2.7. 1-N,N-Dimethylamino-5-phenyl-5H-dibenzophosphole
(3h). Yellow oil (39%). 31P NMR (CDCl3, 161 MHz):
d
(ppm)¼ꢀ9.0.
4.3. 31P{1H} NMR experiments for preparation of phosphole
selenide compounds 6
1H NMR (300 MHz, CDCl3):
d
(ppm)¼8.62 (d, J¼8.0 Hz, 1H), 7.62
(t, J¼13.1 Hz, 1H), 7.42 (td, J¼8.3, 1.2 Hz, 1H), 7.33 (td, J¼7.1, 1.2 Hz,
1H), 7.3e7.0 (m, 8H), 2.82 (s, 3H), 2.76 (s, 3H). 13C NMR (75 MHz,
To an NMR tube charged with 20 mg of phosphole and 20 mg of
selenium was added 1 mL of CDCl3. Samples were kept under ar-
gon during 24 h before being analyzed in 31P{1H} NMR experi-
ments. 31P NMR shifts and 31Pe77Se coupling constants are
reported in Table 2.
CDCl3):
d
(ppm)¼152.0, 145.2 (d, J¼1.2 Hz), 143.9 (d, J¼2.9 Hz), 142,
7, 136.9 (d, J¼19.9 Hz), 136.2 (d, J¼3.1 Hz), 133.8 (d, J¼19.5 Hz),
133.9, 133.7, 129.8 (d, J¼22.1 Hz), 129.3, 128.7e128.4 (2C), 128.0 (d,
J¼9.0 Hz), 126.6 (d, J¼8.0 Hz), 126.4, 124.9 (d, J¼22.6 Hz), 119.1, 45.4,
44.0. MS(EI): m/z(%)¼303.1 (100) [Mþ], 262.1 (51) [MþꢀNMe2],
183.1 (40) [MþꢀNMe2ꢀPh].
4.4. General procedure for the catalytic hydroformylation
reactions
4.2.8. 1-Trifluoromethoxy-5-phenyl-5H-dibenzophosphole
(3i). Colorless solid (61%). Mp 50e51 ꢁC. 31P NMR (161 MHz,
CDCl3):
d
(ppm)¼ꢀ7.4. 1H NMR (300 MHz, CDCl3):
d
(ppm)¼8.30
The catalyst precursor [Rh(CO)2acac] (0.0236 mmol) and the
ligand (0.0473 mmol) were dissolved in 30 mL of toluene under
nitrogen. The substrate (23.6 mmol) and the internal standard
(5.13 mmol of decane) were added to the solution. The reaction
mixture was transferred into the autoclave 90 mL inox (TOP
INDUSTRIE), which was flushed several times with H2/CO gas, and
the mixture was stirred at 200 rpm at room temperature. The au-
toclave was pressurized to an initial 10 bar pressure of syngas (CO/
H2¼1:1), heated to the required temperature and then pressurized
at 30 bar. The reaction mixture was stirred at 1000 rpm for the
desired time and the pressure was adjusted to 30 bar permanently.
After the catalytic reaction, the autoclave was then cooled and
slowly depressurized. A sample was analyzed by GC (PerkineElmer
StabilwaxÒ-AD equipped with a column (30 m length, 0.25 mm
(d, J¼8.2 Hz, 1H), 7.65 (t, J¼6.7 Hz, 1H), 7.6e7.5 (m, 1H), 7.45
(td, J¼7.7, 1.3 Hz, 1H), 7.1e7.4 (m, 8H). 13C NMR (75 MHz, CDCl3):
d
(ppm)¼146.2 (d, J¼3.9 Hz), 145.9 (d, J¼1.0 Hz), 142.8
(d, J¼1.9 Hz), 141.4 (d, J¼1.8 Hz), 135.4 (d, J¼19.3 Hz), 135.2
(d, J¼3.6 Hz), 132.9 (d, J¼20.5 Hz, 2C), 130.3 (d, J¼22.5 Hz),
129.2 (d, J¼0.9 Hz), 129.1, 128.9e128.5 (m, 3C), 128.2 (d, J¼8.5 Hz),
128.0 (d, J¼8.1 Hz), 126.0, 120.9 (q, J¼257.0 Hz), 120.7 (2C). MS(EI):
m/z(%)¼344.1 (100) [Mþ], 275.1 (38) [Mþꢀ3 F], 257.1 (48)
[MþꢀOCF3], 170.1 (58) [Mþꢀ3 FꢀPPh]. HRMS for C19H12NaOP:
calcd 367.0470; found 367.0510.
4.2.9. 6-Phenyl-6H-benzo[2,3]phosphindolo[4,5-d][1,3]dioxole
(4a). Yellow oil (96%). 31P NMR (161 MHz, CDCl3):
d
(ppm)¼ꢀ5.5.
1H NMR (300 MHz, CDCl3):
d
(ppm)¼8.02 (dd, J¼7.7, 0.6 Hz, 1H),
inner diameter and 0.25
and FID detector).
mm film thickness), 14 psi He as carrier gas
7.6e7.5 (m,1H), 7.38 (td, J¼7.5, 1.2 Hz,1H), 7.3e7.0 (m, 7H), 6.77 (dd,
J¼7.8, 2.4 Hz, 1H), 6.07 (s, 2H). 13C NMR (75 MHz, CDCl3):
(ppm)¼
d
148.8, 143.0e142.9 (m, 2C), 141.2 (d, J¼1.4 Hz), 137.1 (d, J¼20.5 Hz),
135.3 (d, J¼2.7 Hz), 132.4 (d, J¼20.2 Hz, 2C), 130.2 (d, J¼22.0 Hz),
129.2, 128.8e128.6 (m, 3C), 127.4 (d, J¼7.7 Hz), 126.4 (d, J¼3.8 Hz),
124.7, 123.8 (d, J¼24.3 Hz), 108.1 (d, J¼8.8 Hz), 101.6. MS(EI): m/
z(%)¼304.1 (100) [Mþ], 274.2 (47) [MþꢀOCH2], 227.1 (24) [MþꢀPh],
Acknowledgements
ꢁ
We thank the CNRS, the Ministere de la Recherche of France, the
LIA-229 (French Moroccan Associated Laboratory) and are very
much grateful to LONZA, Switzerland for financial support to LB.