J
H. Szabó-Szentjóbi et al.
Paper
Synthesis
IR (KBr): 3364, 3242, 3066, 2969, 2930, 2873, 1589, 1575, 1501, 1474,
1441, 1374, 1345, 1282, 1241, 1177, 1134, 1109, 1086, 1069, 1045,
Reduction of Phosphine Oxides; General Procedure
Phosphine oxide and silane (1.5 mL for 100 mg phosphine oxide)
were mixed with vigorous stirring in a sealed tube under argon. The
temperature of the reaction mixture was raised to 150 °C and kept
stirring at this temperature for 3 days. The volatile components were
removed, and the crude product was purified by PLC on silica gel as
described below for each compound.
1023, 967, 833, 757, 700, 555, 505 cm–1
.
1H NMR (300 MHz, CDCl3): = 0.90 (d, J = 6.3 Hz, 6 H, CH3), 0.98 (d, J =
6.4 Hz, 6 H, CH3), 2.29 (pent, J = 6.1 Hz, 2 H, CH2), 2.78–2.83 (m, 2 H),
3.11–3.15 (m, 4 H), 3.21–3.26 (m, 2 H), 3.37–3.53 (m, 10 H), 3.58–3.62
(m, 2 H), 3.68–3.72 (m, 2 H), 3.80–3.83 (m, 2 H), 3.99–4.02 (m, 2 H),
4.12–4.22 (m, 6 H, OCH, OCH2), 6.93–7.05 (m, 12 H, ArH), 7.37–7.46
(m, 6 H, ArH), 7.81–7.85 (m, 2 H, ArH), 7.90–7.94 (m, 4 H, ArH).
13C NMR (75 MHz, CDCl3): = 17.03, 17.51 (CH3), 29.08 (CH2), 64.26,
69.58, 69.92, 71.23, 71.42, 71.93, 72.95, 75.08, 75.42 (OCH, OCH2),
112.27 (d, J = 6.5 Hz, ArC), 112.83 (d, J = 6.2 Hz, ArC), 114.07 (d, J =
13.4 Hz, ArC), 115.47 (ArC), 120.44 (d, J = 11.3 Hz, ArC), 120.54 (d, J =
10.8 Hz, ArC), 122.29 (d, J = 108 Hz, ArC), 123.54 (d, J = 108 Hz, ArC),
124.88 (d, J = 115 Hz, ArC), 128.91 (ArC), 132.77 (ArC), 132.96 (d, J =
1.7 Hz, ArC), 133.69, 133.76, 133.80, 133.86, 133.90 (ArC), 159.94 (d,
J = 3.2 Hz, ArC), 160.82 (d, J = 2.3 Hz, ArC), 161.15 (d, J = 2.9 Hz, ArC).
(6S,7S)-6,7-Dimethyl-13-phenyl-7,13-dihydro-6H-dibenzo[e,h]-
[1,4,7]dioxaphosphine [(S,S)-3]
Phosphine (S,S)-3 was prepared from phosphine oxide (S,S)-21
(180 mg, 0.49 mmol) using trimethoxysilane as a reducing agent. The
eluent was EtOAc/hexane (1:8). Phosphine (S,S)-3 (150 mg, 88%) was
obtained as white crystals; mp 149–152 °C; Rf = 0.50 (EtOAc/hexane
1:4); []D23 –123.6 (c 0.3 CH2Cl2).
IR (KBr): 3140, 3058, 2965, 2867, 2052, 1901, 1795, 1583, 1570, 1469,
1440, 1384, 1376, 1271, 1236, 1130, 1091, 1073, 1029, 945, 837, 762,
31P NMR (121.5 MHz, CDCl3): = 23.55.
613, 540, 497, 468 cm–1
.
HRMS (ESI): m/z [M + H]+ calcd for C59H71O14P2: 1065.4314; found:
1065.4278.
1H NMR (500 MHz, CDCl3): = 1.23 (d, J = 6.1 Hz, 3 H, CH3), 1.48 (d, J =
6.3 Hz, 3 H, CH3), 4.07–4.18 (m, 2 H, OCH), 6.90–6.93 (m, 2 H, ArH),
6.99–7.04 (m, 2 H, ArH), 7.11–7.14 (m, 1 H, ArH), 7.19–7.22 (m, 1 H,
ArH), 7.26–7.29 (m, 1 H, ArH), 7.34–7.37 (m, 1 H, ArH), 7.43–7.46 (m,
3 H, ArH), 7.72–7.75 (m, 2 H, ArH).
13C NMR (75 MHz, CDCl3): = 17.46, 18.54 (CH3), 84.62, 87.22 (OCH),
120.36 (d, J = 2.1 Hz, ArC), 123.60 (d, J = 3.1 Hz, ArC), 123.70 (d, J = 8.7
Hz, ArC), 128.66 (d, J = 8.9 Hz, ArC), 129.27, 129.80, 130.92, 133.79 (d,
J = 0.8 Hz, ArC), 133.92 (d, J = 13.5 Hz, ArC), 135.98, 136.29, 161.25 (d,
J = 6.1 Hz, ArC), 164.90 (d, J = 16.3 Hz, ArC).
(7S,7′S,15S,15′S)-22,22′-{[Butane-1,4-diylbis(oxy)]bis(4,1-phenyl-
ene)}bis(7,15-dimethyl-7,9,10,12,13,15,16,22-octahydro-22H-
225-dibenzo[n,q][1,4,7,10,13,16]pentaoxaphosphacycloocta-
decin-22-one) [(S,S,S,S)-32]
Macrocycle (S,S)-30 (300 mg, 0.59 mmol), pure and anhyd DMF
(10 mL), and finely powdered anhyd K2CO3 (500 mg, 3.62 mmol) were
placed under argon in a three-necked flask fitted with a stirring bar
and a dropping funnel. This mixture was stirred for 30 min, and
cooled to 0 °C, and 1,4-dibromobutane (65.0 mg, 0.30 mmol)
dissolved in anhyd and pure DMF (15 mL) was added dropwise. The
resulting mixture was warmed up to 50 °C and stirred for 3 days. The
solvent was removed, then the residue was dissolved in a mixture of
H2O (20 mL) and CH2Cl2 (20 mL). The phases were shaken well and
separated. The aqueous phase was extracted with CH2Cl2 (3 × 15 mL).
The combined organic phases were dried (MgSO4), filtered, and the
solvent was removed. The crude product was purified by PLC on silica
gel using MeOH/CH2Cl2 (1:20) as eluent to give (S,S,S,S)-32 (226 mg,
71%) as a colorless oil; Rf = 0.28 (CH2Cl2/ MeOH 20:1); []D27 +36.2 (c
0.87, CH2Cl2).
31P NMR (121.5 MHz, CDCl3): = –19.26.
HRMS (ESI): m/z [M + H]+ calcd for C22H22O2P: 349.1335; found:
349.1352.
(7R,12R)-7,12-Dimethyl-19-phenyl-6,7,9,10,12,13-hexahydro-
19H-195-dibenzo[k,n][1,4,7,10,13]tetraoxaphosphacyclopenta-
decine [(R,R)-4]
Phosphine (R,R)-4 was prepared from phosphine oxide (R,R)-22
(300 mg, 0.66 mmol) using trimethoxysilane. The eluent was CH2Cl2/
MeOH (80:1). Phosphine (R,R)-4 (230 mg, 80%) was obtained as white
crystals; mp 124–126 °C; Rf = 0.60 (CH2Cl2/MeOH 30:1); []D21 –107.1
(c 0.7 CH2Cl2).
IR (neat): 3065, 2967, 2930, 2872, 1589, 1574, 1501, 1475, 1441,
1376, 1345, 1281, 1244, 1177, 1134, 1109, 1022, 968, 830, 756, 693,
IR (KBr): 3140, 3056, 2969, 2926, 2871, 2532, 2052, 1959, 1915, 1823,
1791, 1704, 1583, 1572, 1470, 1440, 1385, 1375, 1346, 1321, 1273,
1226, 1131, 1092, 1073, 1027, 924, 910, 858, 835, 818, 762, 689, 609,
555, 505 cm–1
.
1H NMR (300 MHz, CDCl3): = 0.90 (t, J = 6.3 Hz, 3 H, CH3), 0.97 (t, J =
6.3 Hz, 3 H, CH3), 1.97–2.01 (m, 4 H), 2.79–2.83 (m, 2 H), 3.10–3.27
(m, 6 H), 3.35–3.53 (m, 10 H), 3.57–3.72 (m, 4 H), 3.78–3.83 (m, 2 H),
3.98–4.16 (m, 8 H, OCH, OCH2), 6.91–7.06 (m, 12 H, ArH), 7.36–7.47
(m, 6 H, ArH), 7.80–7.95 (m, 6 H, ArH).
13C NMR (75 MHz, CDCl3): = 17.09, 17.58 (CH3), 25.92 (CH2), 67.46,
69.63, 69.99, 71.28, 71.47, 71.99, 73.01, 75.13, 75.47 (OCH, OCH2),
112.44 (d, J = 8.1 Hz, ArC), 112.88 (d, J = 5.5 Hz, ArC), 114.09 (d, J =
13.7 Hz, ArC), 120.44 (d, J = 8.1 Hz, ArC), 120.60 (d, J = 7.2 Hz, ArC),
122.36 (d, J = 94 Hz, ArC), 123.59 (d, J = 65 Hz, ArC), 124.98 (d, J = 84
Hz, ArC), 132.85 (d, J = 15.0 Hz, ArC), 133.76 (d, J = 7.0 Hz, ArC), 133.89
(d, J = 9.4 Hz, ArC), 159.96 (d, J = 2.9 Hz, ArC), 160.87 (d, J = 2.1 Hz,
ArC), 161.34 (d, J = 2.8 Hz, ArC).
524, 506, 496, 469, 425, 413 cm–1
.
1H NMR (500 MHz, CD3CN): = 1.07–1.10 (m, 6 H, CH3), 2.87–3.21 (m,
4 H) 3.52–3.72 (m, 4 H), 4.00–4.18 (m, 2 H, OCH, OCH2), 6.94–7.03 (m,
3 H, ArH), 7.06–7.11 (m, 1 H, ArH), 7.39–7.47 (m, 5 H, ArH), 7.53–7.61
(m, 1 H, ArH), 7.69–7.77 (m, 1 H, ArH), 8.05–8.12 (m, 2 H, ArH).
13C NMR (75 MHz, CD3CN): = 15.86, 16.42 (CH3), 68.41 (d, J = 1.9 Hz),
69.39 (d, J = 6.1 Hz), 72.33 (d, J = 1.3 Hz), 73.24, 74.45 (d, J = 1.2 Hz),
75.46 (OCH, OCH2), 111.80 (d, J = 1.5 Hz, ArC), 112.15 (d, J = 2.2 Hz,
ArC), 120.96 (d, J = 8.0 Hz, ArC), 125.46 (d, J = 13.8 Hz, ArC), 126.58 (d,
J = 15.5 Hz, ArC), 128.50, 128.60 (d, J = 1.1 Hz, ArC), 133.52 (d, J = 0.8
Hz, ArC), 133.81, 134.06 (d, J = 2.2 Hz, ArC), 134.09, 136.95 (d, J = 14.3
Hz, ArC), 160.09 (d, J = 17.3 Hz, ArC), 161.33 (d, J = 18.8 Hz, ArC).
31P NMR (121.5 MHz, CD3CN): = –32.73.
31P NMR (121.5 MHz, CDCl3): = 23.44.
HRMS (ESI): m/z [M + H]+ calcd for C26H30O4P: 437.1876; found:
HRMS (ESI): m/z [M + H]+ calcd for C60H73O14P2: 1079.4470; found:
437.1854.
1079.4426.
© 2020. Thieme. All rights reserved. Synthesis 2020, 52, A–M