X. Zhang et al.
8.1 Hz, 4H), 7.232 (dt, J1 =9.9 Hz, J2 =2.6 Hz, 4H), 7.107 (dt, J1 =8.7 Hz,
J2 =2.7 Hz, 4H), 6.983 ppm (s, 2H); 13C NMR (100 MHz, DMSO): d=
161.3 (dd, JCF =245.0, 11.4), 159.7 (dd, JCF =248.1, 12.2), 153.7, 133.6 (dd,
0.2 mmol), and DMF (25 mL) were added to a 125 mL flask. Allyl chlo-
ride (0.44 mL, 5.4 mmol) was added dropwise over 10 min. The reaction
mixture was stirred at room temperature for 12 h. The reaction was
quenched by water (20 mL) and was stirred at 08C for 10 min. The result-
ing precipitate was filtered off, washed with water, and recrystallized
from ethanol to yield the desired product (0.9 g, 90%). 1H NMR
(400 MHz, CDCl3): d=7.861 (m, 2H), 7.725 (m, 2H), 5.894 (m,1H),
5.255 (dd, J1 =16.8 Hz, J2 =1.3 Hz, 1H), 5.199 (dd, J1 =10.5 Hz, J2 =
1.3 Hz, 1H), 4.301 ppm (d, J=5.6 Hz, 2H); 13C NMR (100 MHz, CDCl3):
d=167.9, 134.0, 132.2, 131.6, 123.3, 117.8, 40.1 ppm.
J
CF =9.4, 5.2), 132.6, 122.7, 114.2, 111.1 (dd, JCF =20.8, 3.2), 110.1,
103.8 ppm (t,
À112.7 ppm.
J
CF =26.3); 19F NMR (376.5 MHz, DMSO): d=À109.3,
Synthesis of 3,3’,5,5’-tetra(4-methoxyphenyl)-1,1’-biphenyl-2,2’,6,6’-tetraol
(7c): Compound 6c (1.75 g, 5.8 mmol), CH2Cl2 (16 mL), and MeOH
(24 mL) were added to a 250 mL flask, followed by 36% concentrated
HCl (16 mL). The reaction mixture was stirred and refluxed for 6 h.
After that, the reaction mixture was concentrated, diluted with 20 mL
water and extracted with CH2Cl2 (3ꢂ50 mL). The combined organic
layers were dried over Na2SO4, and passed through a small pad of silica
gel. The solvent was then removed under reduced pressure to afford the
tetraol product 7c as a white solid (1.3 g, 95%). 1H NMR (400 MHz,
CDCl3): d=7.508 (d, J=8.4 Hz, 8H), 7.346 (s, 2H), 6.989 (d, J=8.8 Hz,
8H), 5.428 (s, 4H), 3.848 ppm (s, 12H); 13C NMR (100 MHz, CDCl3): d=
159.0, 150.7, 132.9, 130.4, 129.3, 121.5, 114.3, 105.3, 55.4 ppm.
Synthesis of 4-(1,3-dioxoisoindolin-2-yl)butanal (Table 2, entry 7): The
typical hydroformylation procedure was followed. Once the reaction was
complete, the solvent was removed under vacuum. The resultant crude
product was subjected to flash column chromatography (silica gel, 25%
EtOAc/Hexane). 1H NMR (400 MHz, CDCl3): d=9.779 (t, J=1.2 Hz,
1H), 7.840 (m, 2H), 7.733 (m, 2H), 3.742 (t, J=7.2 Hz, 2H), 2.556 (dt,
J1 =7.3 Hz, J2 =1.2 Hz, 2H), 2.030 ppm (m, 2H); 13C NMR (100 MHz,
CDCl3): d=200.8, 168.3, 134.0, 132.0, 123.2, 41.0, 37.1, 21.1 ppm.
Synthesis of 3-(1,3-dioxoisoindolin-2-yl)propanal (Table 3, entry 7): The
typical hydroformylation procedure was followed. Once the reaction was
complete, the solvent was removed under vacuum. The resulted crude
product was subjected to flash column chromatography (silica gel, 25%
EtOAc/Hexane). 1H NMR (400 MHz, CDCl3): d=9.828 (t, J=1.2 Hz,
1H), 7.837 (m, 2H), 7.731 (m, 2H), 4.035 (t, J=7.0 Hz, 2H), 2.893 ppm
(dt, J1 =7.1 Hz, J2 =1.4 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=199.4,
168.0, 134.1, 132.0, 123.4, 42.4, 31.7 ppm.
Synthesis of 3,3’,5,5’-tetra(4-chlorophenyl)-2,2’,6,6’-tetra((di-1-pyrrolyl-
phosphino)oxy)-1,1’-biphenyl (2): A solution of triethylamine (1.4 mL) in
THF (10 mL) and a solution of compound 7a (1.321 g, 2 mmol) in THF
(30 mL) at room temperature were added dropwise to a solution of chlor-
odipyrrolyphosphine (8.8 mmol, 1.75 g) in THF (10 mL). The Et3N.HCl
salts were formed immediately after the addition. The reaction mixture
was stirred overnight (ꢁ12 h) at room temperature. The Et3N.HCl salts
were then filtered off and the solvent was removed under vacuum. The
crude product was recrystallized from hexane to afford the title ligand 2
as a white solid (0.51 g, 20%). 1H NMR (400 MHz, CDCl3): d=7.069 (s,
2H), 7.066 (d, J=8.5 Hz, 8H), (s, 2H), 6.893 (d, J=8.5 Hz, 8H), 6.517 (s,
16H), 6.098 ppm (t, J=2.1 Hz, 16H); 13C NMR (100 MHz, CDCl3): d=
149.6, 134.6, 134.5, 134.0, 130.7, 130.6, 128.4, 120.8, 120.3, 112.1 ppm;
31P NMR (162 MHz, CDCl3): d=105.7; HRMS (ES+) calcd for
C68H51N8O4P4Cl4: 1307.1738 [M]+; found: 1307.1609.
Acknowledgements
We thank the National Science Foundation (NSF CHE# 0956784) and
Dow Chemical Inc. for financial support. The Bruker 400 MHz NMR
spectrometer used in this study was purchased with grant no.:
1S10RR023698–01A1 from the National Center for Research Resources
(NCRR), a component of the NIH. We thank Dr. Furong Sun for HRMS
analyses.
Synthesis of 3,3’,5,5’-tetra(2,4-difluorophenyl)-2,2’,6,6’-tetra((di-1-pyrro-
lylphosphino)oxy)-1,1’-biphenyl (3): A solution of triethylamine (1.4 mL)
in THF (10 mL) and a solution of compound 7b (1.333 g, 2 mmol) in
THF (30 mL) at room temperature were added dropwise to a solution of
chlorodipyrrolyphosphine (8.8 mmol, 1.75 g) in THF (10 mL). The
Et3N·HCl salts were formed immediately after the addition. The reaction
mixture was stirred overnight (ꢁ12 h) at room temperature. The
Et3N·HCl salts were then filtered off and the solvent was removed under
vacuum. The crude product was recrystallized from hexane to afford the
[1] For recent reviews and monographs, see: a) Rhodium Catalyzed Hy-
droformylation (Eds.: C. Claver, P. W. N. M. van Leeuwen), Kluwer
Academic Publishers, Dordrecht, 2000; b) F. Ungvꢃry, Coord. Chem.
Rev. 2005, 249, 2946–2961; c) M. L. Clarke, Curr. Org. Chem. 2005,
9, 701; d) M. Diꢄguez, O. Pamies, C. Claver, Tetrahedron: Asymme-
[2] a) R. Jennerjahn, I. Piras, R. Jackstell, R. Franke, K.-D. Wiese, M.
c) G. Makado, T. Morimoto, Y. Sugimoto, K. Tsutsumi, N. Kagawa,
131, 649; f) W. Liu, M. Yuan, H. Fu, H. Chen, R. Li, X. Li, Chem.
261; i) A. D. Worthy, M. M. Gagnon, M. T. Dombrowski, K. L. Tan,
[3] a) T. J. Devon, G. W. Phillips, T. A. Puckette, J. L. Stavinoha, J. J.
Vanderbilt, US 4694109, 1987; b) W. A. Herrmann, C. W. Kohlpaint-
Casey, G. T. Whiteker, M. G. Melville, L. M. Lori, J. A., Jr. Gavney,
mann, R. Schmidt, C. W. Kohlpaintner, T. Priermeier, Organometal-
ler, B. R. Proft, L. M. Petrovich, B. A. Matter, D. R. Powell, J. Am.
1
title ligand 3 as a white solid (0.95 g, 36%). H NMR (400 MHz, CDCl3):
d=7.168 (s, 2H), 6.706 (dt, J1 =9.4 Hz, J2 =2.4 Hz, 4H), 6.638 (m, 4H),
6.554 (m, 4H), 6.530 (s, 16H), 6.079 ppm (t, J=2.1 Hz, 16H); 13C NMR
(100 MHz, CDCl3): d=163.2 (dd, JCF =250.9, 12.6 Hz), 160.3 (dd, JCF
=
250.0, 12.6 Hz), 151.2, 136.2, 133.1 (dd, JCF =10.1, 4.0 Hz), 124.5, 121.0,
120.2, 119.8 (dd, JCF =15.1, 3.0 Hz), 112.1, 111.4 (dd, JCF =21.1, 4.0 Hz),
104.1 ppm (t, JCF =24.7 Hz); 31P NMR (162 MHz, CDCl3): d=105.8 ppm;
19F NMR (376.5 MHz, CDCl3): d=À108.7, À109.8 ppm; HRMS (ES+)
calcd for C68H47N8O4F8P4: 1315.2543 [M]+; found: 1315.2672.
Synthesis of 3,3’,5,5’-tetra(4-methoxyphenyl)-2,2’,6,6’-tetra((di-1-pyrrolyl-
phosphino)oxy)-1,1’-biphenyl (4): A solution of triethylamine (1.4 mL) in
THF (10 mL) and a solution of compound 7c (1.285 g, 2 mmol) in THF
(30 mL) were added dropwise to a solution of chlorodipyrrolyphosphine
(8.8 mmol, 1.75 g) in THF (10 mL) at room temperature. The Et3N·HCl
salts were formed immediately after the addition. The reaction mixture
was stirred overnight (ꢁ12 h) at room temperature. The Et3N·HCl salts
were then filtered off and the solvent was removed under vacuum. The
crude product was recrystallized from hexane to afford the title ligand 4
as a white solid (0.75 g, 29%). 1H NMR (400 MHz, CDCl3): d=7.155 (s,
2H), 7.020 (d, J=8.4 Hz, 8H), 6.668 (d, J=8.8 Hz, 8H), 6.510 (s, 16H),
6.061 (t, J=2.0 Hz, 16H), 3.806 ppm (s, 12H); 13C NMR (100 MHz,
CDCl3): d=159.0, 134.8, 130.9, 130.7, 128.9, 121.0, 120.9, 120.8, 113.8,
111.7, 55.3 ppm; 31P NMR (162 MHz, CDCl3): d=105.7; HRMS (ES+)
calcd for C72H63N8O8P4: 1291.3719 [M]+; found: 1291.3721.
Synthesis of N-allylphthalimide (Table 2, entry 7 olefin): Potassium
phthalimide (1.0 g, 5.4 mmol), tetrabutylammonium bromide (30 mg,
[4] a) M. Kranenburg, Y. E. M. van der Burgt, P. C. J. Kamer,
&
6
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ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 0000, 00, 0 – 0
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