C. Recsei, C.S.P. McErlean / Tetrahedron 68 (2012) 464e480
477
4.29. 3,30-Bis(1-(p-methoxyphenyl)-1H-1,2,3-triazol-4-yl)-1,10-
binaphthyl-2,20-diyl 1-pyrrolidylphosphonite (27b) and 3,30-
bis(1-(p-methoxyphenyl)-1H-1,2,3-triazol-4-yl)-1,10-binaphth
yl-2,20-diyl 1-pyrrolidylphosphonate (28b)
dichloromethane (20 mL). The aqueous phase was extracted with
dichloromethane (3ꢂ20 mL) and the combined organic phases
were washed with saturated aqueous ammonium chloride (50 mL),
brine (50 mL), were dried over anhydrous sodium sulfate and the
solvent was evaporated. Flash column chromatography (ethyl ac-
etate/hexanes: 1/1) gave 27c (37 mg, 66%) as a colourless solid. Rf
0.23 (ethyl acetate/hexanes: 1/3); IR (neat) nmax/cmꢀ1 3312, 2967,
1421, 1054, 905; 1H NMR (300 MHz; CDCl3) 9.27 (1H, s), 8.97 (1H, s),
8.91 (1H, s), 8.89 (1H, s), 8.23 (2H, d, J 6.8), 8.22 (2H, d, J 6.8), 7.99
(2H, d, J 8.7), 7.81e7.93 (6H, m), 7.51e7.58 (2H, m), 7.36e7.43 (2H,
m), 7.20e7.27 (2H, m), 2.59e2.71 (2H, m), 2.71e2.80 (2H, m),
1.29e1.34 (4H, m); 31P NMR (121 MHz; CDCl3) 149.1; MS (ESI) m/e
(relative intensity) 828 (44), 830 (100), 831 (40), 832 (57); HRMS
(ESI) obsd 830.0502 (MHþ) calcd 830.0467 and the corresponding
phosphoramidate 28c (16 mg, 28%); Rf 0.16 (ethyl acetate/hexanes:
1/3); IR (neat) nmax/cmꢀ1 2952,1428,1411,1060; 1H NMR (300 MHz;
CDCl3) 9.15 (1H, s), 9.09 (1H, s), 8.84 (1H, s), 8.79 (1H, s), 8.18 (1H, d,
J 8.6), 8.11 (1H, d, J 8.6), 7.86e8.11 (2H, m), 7.59e7.65 (8H, m),
7.24e7.41 (4H, m), 2.73e2.89 (2H, m), 2.57e2.68 (2H, m), 1.31e1.47
(4H, m); 31P NMR (121 MHz; CDCl3) 11.8; MS (ESI) m/e (relative
intensity) 844 (50), 846 (100), 847 (43), 848 (60); HRMS (ESI) obsd
846.0507 (MHþ) calcd 846.0416.
Phosphorus trichloride (320 mL, 3.67 mmol) was added to
a stirred solution of 26b (230 mg, 3.64ꢂ10ꢀ4 mol) in a 3:2 mixture
of toluene/m-dichlorobenzene (15 mL) and the reaction mixture
was heated to 110 ꢁC for 8 h. The mixture was cooled to 0 ꢁC and
pyrrolidine (1.20 mL, 14.6 mmol) was added slowly. The mixture
was stirred at 0 ꢁC for 15 min, then allowed to warm to room
temperature and stirred for an additional 1 h. The reaction mixture
was partitioned between saturated aqueous ammonium chloride
(50 mL) and dichloromethane (30 mL). The aqueous phase was
extracted with dichloromethane (3ꢂ30 mL) and the combined or-
ganic phases were washed with saturated aqueous ammonium
chloride (100 mL), brine (100 mL), were dried over anhydrous so-
dium sulfate and the solvent was evaporated. Flash column chro-
matography (ethyl acetate/hexanes: 3/2) gave 27b (64 mg, 24%) as
a colourless powder. Mp>140 ꢁC (decomposes); Rf 0.35 (ethyl ac-
etate/hexanes: 3/2); IR (neat) nmax/cmꢀ1 2967, 1519, 1261, 1035,
796; 1H NMR (300 MHz; CDCl3) 9.04 (1H, s), 8.95 (1H, s), 8.57 (1H,
s), 8.36 (1H, s), 8.07 (2H, d, J 6.5) 7.65e7.71 (4H, m), 7.45e7.49 (2H,
m), 7.27e7.39 (4H, m), 7.03e7.07 (4H, m), 3.87 (3H, m), 3.87 (3H,
m), 2.82e2.91 (2H, m), 2.71e2.80 (2H, m), 1.42e1.49 (4H, m); 13C
NMR (75 MHz; CDCl3) 160.1 (C), 160.0 (C), 147.0 (C, 2JCeP 4.1) 146.3
(C), 144.1 (C), 143.9 (C), 132.7 (CH), 132.6 (CH), 131.4 (C), 130.9 (C),
130.8 (C), 130.7 (C), 129.1 (2C, CH), 128.4 (CH), 128.3 (CH), 126.8
(CH), 126.8 (CH), 126.7 (2C, CH), 125.6 (CH), 125.4 (CH), 125.0 (C),
124.9 (C), 124.0 (C), 124.0 (C), 123.1 (C), 123.0 (C), 122.3 (2C, CH),
122.2 (2C, CH), 121.6 (CH), 121.2 (CH), 121.2 (CH), 115.1 (2C, CH),
115.0 (2C, CH), 55.8 (2C, CH3), 45.6 (2C, CH2, d, 2JCeP 16.8), 25.7 (2C,
4.31. 3,30-Bis(1-(p-fluorophenyl)-1H-1,2,3-triazol-4-yl)-1,10-
binaphthyl-2,20-diyl 1-pyrrolidylphosphonite (27d) and 3,30-
bis(1-(p-fluorophenyl)-1H-1,2,3-triazol-4-yl)-1,10-binaphthyl-
2,20-diyl 1-pyrrolidylphosphonite (28d)
Phosphorus trichloride (55 mL, 6.3 mmol) was added to a stirred
solution of 27g (40 mg, 63ꢂ10ꢀ5 mol) in toluene (3 mL) and the
reaction mixture heated to 110 ꢁC for 15 h. The mixture was cooled
to 0 ꢁC and pyrrolidine (0.20 mL, 2.4 mmol) was added slowly. The
mixture was stirred at 0ꢁ C for 15 min, then allowed to warm to
room temperature and stirred for a further 1 h. The reaction mix-
ture was partitioned between saturated aqueous ammonium
chloride (30 mL) and dichloromethane (10 mL). The aqueous phase
was extracted with dichloromethane (3ꢂ10 mL) and the combined
organic layers were washed with saturated aqueous ammonium
chloride (50 mL), brine (50 mL), were dried over anhydrous sodium
sulfate and the solvent was evaporated. Flash column chromatog-
raphy (ethyl acetate/hexanes: 1/4) gave 22g (31 mg, 68%) as a col-
ourless powder. Mp 130 ꢁC (decomposes); Rf 0.22 (ethyl acetate/
hexanes: 1/4); 1H NMR (300 MHz; CDCl3) 9.04 (1H, s), 8.96 (1H, s),
8.62 (1H, s), 8.39 (1H, s), 8.08 (2H, d, J 8.0), 7.71e7.83 (4H, m),
7.46e7.51 (2H, m), 7.22e7.40 (10H, m), 2.80e2.87 (2H, m),
2.73e2.80 (2H, m), 1.43e1.49 (4H, m); 13C NMR (75 MHz; CDCl3)
162.6 (CF, d, 1JCeF 249.4), 162.5 (CF, d, 1JCeF 249.2), 146.9 (C, 2JCeP 4.1)
146.2 (C, 2JCeP 1.4), 144.4 (C), 144.2 (C), 133.6 (C, 4JCeF 3.2), 133.4 (C,
4JCeF 3.1), 132.7 (C, 3JCeP 6.8), 133.6 (C, 3JCeP 5.9), 131.3 (C), 130.9 (C),
129.1 (2C, CH), 128.5 (CH), 128.4 (CH), 126.8 (CH), 126.8 (CH), 125.6
3
CH2, d, JCeP 4.2); 31P NMR (121 MHz; CDCl3) 160.9; MS (ESI) m/e
(relative intensity) 732 (100), 764 (44), 1485 (76); HRMS (ESI) obsd
732.2496 (MHþ) calcd 732.2429, and the corresponding phos-
phoramidate 28b (147 mg, 54%) as a colourless powder. Mp>200 ꢁC
(decomposes); Rf 0.20 (ethyl acetate/hexanes: 3/2); IR (neat) nmax
/
cmꢀ1 2930, 1517, 1253, 1041, 828; 1H NMR (300 MHz; CDCl3) 8.96
(1H, s), 8.94 (1H, s), 8.85 (1H, s), 8.63 (1H, s), 8.08 (1H, d, J 9.1), 8.07
(1H, d, J 9.1), 7.75 (1H, d, J 9.0), 7.72 (1H, d, J 9.0), 7.49e7.56 (2H, m),
7.22e7.34 (4H, m), 7.03 (2H, d, J 9.0), 3.87 (3H, s), 3.84 (3H, s),
2.65e2.73 (2H, m), 2.63e2.56 (2H, m), 1.38e1.49 (4H, m); 13C NMR
(75 MHz; CDCl3) 160.2 (C), 159.9 (C), 144.2 (C, d, 2JCeP 11.7), 143.8 (C,
2
d, JCeP 11.0), 143.0 (C), 142.9 (C), 132.2 (CH), 132.1 (CH) 131.6 (C),
131.6 (C), 130.9 (C), 130.6 (CH), 130.4 (C), 129.2 (CH), 129.2 (CH),
129.1 (CH), 127.4 (CH), 127.2 (2C, CH), 127.0 (CH), 126.6 (CH), 126.3
3
3
3
(CH), 123.1 (C, d, JCeP 3.8), 122.9 (C, d, JCeP 2.8), 122.8 (C, d, JCeP
3.1), 122.4 (CH), 122.3 (2C, CH), 122.3 (2C, CH), 122.0 (C, d, 3JCeP 2.1),
121.6 (CH), 115.1 (2C, CH), 114.9 (2C, CH), 55.8 (2C, CH3), 48.1 (2C,
CH2, d, JCeP 4.7), 26.2 (2C, CH2, d, JCeP 9.6); 31P NMR (121 MHz;
CDCl3) 11.8; MS (ESI) m/e (relative intensity) 748 (100), 770 (77);
HRMS (ESI) obsd 748.2430 (MHþ) calcd 748.2432.
2
3
3
(CH), 125.4 (CH), 124.9 (C), 124.8 (C), 124.0 (C, JCeP 2.1), 122.8 (C,
3
3JCeP 1.8), 122.7 (CH), 122.5 (2C, CH, d, JCeF 8.6), 122.5 (2C, CH, d,
2
3JCeF 8.6), 121.5 (CH), 121.1 (CH), 121.1 (CH), 117.0 (CH, JCeF 23.2),
4.30. 3,30-Bis(1-(p-bromophenyl)-1H-1,2,3-triazol-4-yl)-1,10-
binaphthyl-2,20-diyl 1-pyrrolidylphosphonite (27c) and 3,30-
bis(1-(p-bromophenyl)-1H-1,2,3-triazol-4-yl)-1,10-binaphthyl-
2,20-diyl 1-pyrrolidylphosphonite (28c)
116.9 (CH, 2JCeF 23.2), 45.6 (2C, CH2, d, 2JCeP 15.9), 25.7 (2C, CH2, d,
3JCeP 4.3); 31P NMR (121 MHz; CDCl3) 149.77; 19F NMR (282 MHz;
CDCl3) ꢀ111.85 to ꢀ111.93 (1F, m), ꢀ111.85 to ꢀ111.93 (1F, m); MS
(APCI) m/e (relative intensity) 708 (100), 709 (34); HRMS (ESI) obsd
708.1020 (MHþ) calcd 708.2089, and the corresponding phos-
phoramidate 24g (8.0 mg, 17%) as a colourless powder. Mp 160 ꢁC
(decomposes); Rf 0.14 (ethyl acetate/hexanes: 1/3); 1H NMR
(300 MHz; CDCl3) 9.06 (1H, s), 9.01 (1H, s), 8.88 (1H, s), 8.68 (1H, s),
8.09 (2H, d, J 8.1, 8.1), 7.80e7.89 (4H, m), 7.51e7.59 (2H, m),
7.21e7.41 (10H, m), 2.66e2.75 (2H, m), 2.56e2.64 (2H, m),
Phosphorus trichloride (60
m
L, 70ꢂ10ꢀ4 mol, 10 equiv) was
added to a stirring solution of 26c (50 mg, 6.8ꢂ10ꢀ5 mol) in m-di-
chlorobenzene (5.0 mL) and the reaction mixture was heated to
110 ꢁC for 8 h. The mixture was cooled to 0 ꢁC and pyrrolidine
(220 m
L, 2.68 mmol) added slowly. The mixture was stirred at 0 ꢁC
1
for 15 min, then allowed to warm to room temperature and stirred
for a further 1 h. The reaction mixture was partitioned between
1.37e1.55 (4H, m); 13C NMR (75 MHz; CDCl3) 162.7 (CF, d, JCeF
2
249.6), 162.5 (CF, d, 1JCeF 250.6), 144.0 (C, d, JCeP 9.5), 143.8 (C, d,
saturated
aqueous
ammonium
chloride
(30 mL)
and
2JCeP 9.8), 143.1 (C), 143.0 (C), 133.5 (C, d, 4JCeF 3.1), 133.1 (C, d, 4JCeF