The Journal of Organic Chemistry
Article
(3-Chlorophenyl)diphenylphosphane (26). According to the
general procedure C, reaction with p-methylbenzoyldiphenylphos-
phine 1a (61 mg, 0.20 mmol, 1.0 equiv), 3-chlorophenyl
trifluoromethanesulfonate (54.7 mg, 0.21 mmol, 1.05 equiv), toluene
(0.5 mL), Cs2CO3 (71.7 mg, 0.22 mmol, 1.1 equiv), and PdCl2(dppp)
(5.90 mg, 0.01 mmol, 5 mol %) afforded 26 (42.7 mg) in a yield of
72% as a white amorphous solid. Eluent for silica-gel column
(CDCl3, 162 MHz): δ −5.09. HRMS (ESI-QTOF) m/z: ([M + H]+)
Calcd for C23H25NO2P+ 378.1617; Found 378.1625. IR (film): 3326,
2977, 1728, 1704, 1593, 1454, 1159, 1057, 832, 743, 697, 504 cm−1.
7-(Diphenylphosphanyl)-2H-chromen-2-one (31). According to
the general procedure C, reaction with p-methylbenzoyldiphenyl-
phosphine 1a (61 mg, 0.20 mmol, 1.0 equiv), 2-oxo-2H-chromen-7-yl
trifluoromethanesulfonate (61.8 mg, 0.21 mmol, 1.05 equiv), toluene
(0.5 mL), Cs2CO3 (52.1 mg, 0.16 mmol, 0.8 equiv), and PdCl2(dppp)
(5.90 mg, 0.01 mmol, 5 mol %) afforded 31 (36.3 mg) in a yield of
55% as a white amorphous solid. Eluent for silica-gel column
chromatography: 50/1 to 4/1 PE/EtOAc. 1H NMR (CDCl3, 400
MHz): δ 7.68 (d, J = 9.5 Hz, 1H), 7.45−7.31 (m, 11H), 7.26−7.20
(m, 1H), 7.11 (d, J = 5.8 Hz, 1H), 6.41 (d, J = 9.5 Hz, 1H). 13C{1H}
NMR (CDCl3, 101 MHz): δ 160.5, 153.9 (d, J = 6.2 Hz), 144.1 (d, J
= 16.4 Hz), 143.0, 135.6 (d, J = 10.6 Hz), 134.0 (d, J = 20.2 Hz),
129.5, 129.1 (d, J = 22.8 Hz), 128.9 (d, J = 7.4 Hz), 127.4 (d, J = 8.1
Hz), 121.0 (d, J = 14.8 Hz), 118.6, 117.0. 31P{1H} NMR (CDCl3, 162
MHz): δ −4.18. HRMS (ESI/Q-TOF) m/z: [M + H]+ Calcd for
C21H16O2P+ 331.0882; Found 331.0886. IR (film): 1736, 1604, 1434,
1389, 1173, 1146, 1100, 843, 747, 697 cm−1.
1
chromatography: 100/1 to 30/1 PE/EtOAc. H NMR (CDCl3, 400
MHz): δ 7.36−7.23 (m, 13H), 7.19−7.15 (m, 1H). 31P{1H} NMR
(CDCl3, 162 MHz): δ −4.95. MS (ESI) m/z: [M + H]+ Calcd for
C18H15ClP+ 297; Found 297. IR (film): 3053, 1577, 1559, 1477,
1463, 1433, 1118, 742, 695, 502 cm−1.
Methyl 1-(Diphenylphosphanyl)-2-naphthoate (27). According
to the general procedure C, reaction with p-methylbenzoyldiphenyl-
phosphine 1a (61 mg, 0.20 mmol, 1.0 equiv), methyl 1-
(((trifluoromethyl)sulfonyl)oxy)-2-naphthoate (70.2 mg, 0.21 mmol,
1.05 equiv), toluene (0.5 mL), Cs2CO3 (71.7 mg, 0.22 mmol, 1.1
equiv), PdCl2(dppp) (5.90 mg, 0.01 mmol, 5 mol %) afforded 27
(52.6 mg) in a yield of 71% as a white amorphous solid. Eluent for
silica-gel column chromatography: 50/1 to 20/1 PE/EtOAc. 1H
NMR (CDCl3, 400 MHz): δ 8.18 (dd, J = 8.0, 4.0 Hz, 1H), 7.97 (d, J
= 8.0 Hz, 1H), 7.85 (d, J = 8.0 Hz, 1H), 7.60 (dd, J = 8.0, 4.0 Hz,
1H), 7.45−7.39 (m, 5H), 7.30−7.23 (m, 7H), 3.61 (s, 3H). 13C{1H}
NMR (CDCl3, 101 MHz): δ 170.1 (d, J = 3.4 Hz), 140.5 (d, J = 26.3
Hz), 135.7 (d, J = 12.6 Hz), 134.9 (d, J = 6.8 Hz), 134.4 (d, J = 2.0
Hz), 132.5 (d, J = 18.8 Hz), 131.9 (d, J = 25.6 Hz), 131.3 (d, J = 1.3
Hz), 128.9, 128.6 (d, J = 14.1 Hz), 128.4 (d, J = 6.1 Hz), 128.1, 126.9,
126.6, 124.7 (d, J = 7.4 Hz), 52.2. 31P{1H} NMR (CDCl3, 162 MHz):
δ −9.50. HRMS (ESI-QTOF) m/z: [M + H]+ Calcd for C24H20O2P+
371.1195; Found 371.1199. IR (film): 3052, 1684, 1592, 1478, 1433,
1262, 824, 743, 696, 495 cm−1.
1,4-Bis(diphenylphosphanyl)benzene (32). According to the
general procedure C, reaction with p-methylbenzoyldiphenylphos-
phine 1a (121.7 mg, 0.40 mmol, 2.0 equiv), 1,4-phenylene
bis(trifluoromethanesulfonate) (74.8 mg, 0.2 mmol, 1.0 equiv),
toluene (1.0 mL), Cs2CO3 (143.4 mg, 0.44 mmol, 2.2 equiv), and
PdCl2(dppp) (11.8 mg, 0.02 mmol, 10 mol %) afforded 32 (77.7 mg)
in a yield of 87% as a white amorphous solid. Eluent for silica-gel
1
column chromatography: 100/1 to 30/1 PE/EtOAc. H NMR (400
MHz, CDCl3) δ 7.33−7.29 (m, 20H), 7.24−7.22 (m, 4H). 31P{1H}
NMR (CDCl3, 162 MHz): δ −5.69. HRMS (ESI/Q-TOF) m/z: [M
+
+ H]+ Calcd for C30H25P2 447.1426; Found 447.1427. IR (film):
3051, 1476, 1433, 1090, 1021, 742, 694, 507 cm−1.
3-(Diphenylphosphanyl)pyridine (28). According to the general
procedure C, reaction with p-methylbenzoyldiphenylphosphine 1a
(61 mg, 0.20 mmol, 1.0 equiv), pyridin-3-yl trifluoromethanesulfonate
(47.7 mg, 0.21 mmol, 1.05 equiv), toluene (0.5 mL), Cs2CO3 (71.7
mg, 0.22 mmol, 1.1 equiv), and PdCl2(dppp) (5.90 mg, 0.01 mmol, 5
mol %) afforded 28 (43.2 mg) in a yield of 82% as a white amorphous
solid. Eluent for silica-gel column chromatography: 50/1 to 4/1 PE/
(S)-(2′-Methoxy-[1,1′-binaphthalen]-2-yl)diphenylphosphane
((S)-33). According to the general procedure C, reaction with p-
methylbenzoyldiphenylphosphine 1a (61 mg, 0.20 mmol, 1.0 equiv),
(S)-2′-methoxy-[1,1′-binaphthalen]-2-yl trifluoromethanesulfonate
(90.8 mg, 0.21 mmol, 1.05 equiv), toluene (0.5 mL), Cs2CO3 (71.7
mg, 0.22 mmol, 1.1 equiv), and PdCl2(dppp) (5.90 mg, 0.01 mmol, 5
mol %) afforded (S)-33 (62.8 mg) in a yield of 67% as a white
amorphous solid. Eluent for silica-gel column chromatography: 50/1
to 20/1 PE/EtOAc. [α]D 20−93.9° (CHCl3, c 0.27) (literature
1
EtOAc. H NMR (CDCl3, 400 MHz): δ 8.57 (d, J = 4.0 Hz, 1H),
8.52 (s, 1H), 7.58−7.54 (m, 1H), 7.37−7.24 (m, 11H). 31P{1H}
NMR (CDCl3, 162 MHz): δ −11.76. MS (ESI) m/z: [M + H]+ Calcd
for C17H15NP+ 264; Found 264. IR (film): 3069, 1557, 1478, 1433,
1399, 1089, 1021, 743, 698, 500 cm−1.
12
20
1
rotation for (S)-33 [α]D
−94.5° (CHCl3, c 0.27) ). H NMR
(CDCl3, 400 MHz): δ 7.98 (d, J = 9.0 Hz, 1H), 7.91−7.81 (m, 3H),
7.48−7.42 (m, 1H), 7.39 (dd, J = 8.5, 2.8 Hz, 1H), 7.32−7.03 (m,
15H), 6.93 (d, J = 8.4 Hz, 1H), 3.35 (s, 3H). 31P{1H} NMR (CDCl3,
162 MHz): δ −13.71. MS (ESI) m/z: [M + H]+ Calcd for C33H26OP+
469; Found 469. IR (film): 2927, 1622, 1593, 1434, 1265, 1252, 1038,
1060, 740, 694 cm−1.
4-(Diphenylphosphanyl)quinoline (29). According to the general
procedure C, reaction with p-methylbenzoyldiphenylphosphine 1a
(61 mg, 0.20 mmol, 1.0 equiv), quinolin-4-yl trifluoromethanesulfo-
nate (58.2 mg, 0.21 mmol, 1.05 equiv), toluene (0.5 mL), Cs2CO3
(71.7 mg, 0.22 mmol, 1.1 equiv), and PdCl2(dppp) (5.90 mg, 0.01
mmol, 5 mol %) afforded 29 (59.5 mg) in a yield of 95% as a white
amorphous solid. Eluent for silica-gel column chromatography: 50/1
Naphthalen-1-yldi-p-tolylphosphane (36). According to the
general procedure C, reaction with (di-p-tolylphosphanyl)(phenyl)-
methanone 1b (63.7 mg, 0.20 mmol, 1.0 equiv), naphthalen-1-yl
trifluoromethanesulfonate (58.0 mg, 0.21 mmol, 1.05 equiv), toluene
(0.5 mL), Cs2CO3 (71.7 mg, 0.22 mmol, 1.1 equiv), and PdCl2(dppp)
(5.90 mg, 0.01 mmol, 5 mol %) afforded 36 (49.0 mg) in a yield of
72% as a white amorphous solid. Eluent for silica-gel column
1
to 4/1 PE/EtOAc. H NMR (CDCl3, 400 MHz): δ 8.86 (d, J = 3.3
Hz, 1H), 8.15 (d, J = 8.2 Hz, 1H), 7.81 (d, J = 8.1 Hz, 1H), 7.47−
7.36 (m, 2H), 7.30−7.29 (m, 10H), 7.12 (dd, J = 6.4, 3.7 Hz, 1H).
31P{1H} NMR (CDCl3, 162 MHz): δ −14.94. HRMS (ESI/Q-TOF)
m/z: [M + H]+ Calcd for C21H17NP+ 314.1093; Found 314.1100. IR
(film): 1490, 1432, 828, 794, 743, 696, 553, 498, 457, 424 cm−1.
tert-Butyl (3-(Diphenylphosphanyl)phenyl)carbamate (30). Ac-
cording to the general procedure C, reaction with p-methylbenzoyldi-
phenylphosphine 1a (61 mg, 0.20 mmol, 1.0 equiv), 3-((tert-
butoxycarbonyl)amino)phenyl trifluoromethanesulfonate (71.7 mg,
0.21 mmol, 1.05 equiv), toluene (0.5 mL), Cs2CO3 (71.7 mg, 0.22
mmol, 1.1 equiv), and PdCl2(dppp) (5.90 mg, 0.01 mmol, 5 mol %)
afforded 30 (46.8 mg) in a yield of 62% as a white amorphous solid.
Eluent for silica-gel column chromatography: 50/1 to 10/1 PE/
1
chromatography: 100/1 to 30/1 PE/EtOAc. H NMR (CDCl3, 400
MHz): δ 8.40−8.36 (m, 1H), 7.835 (dd, J = 8.0, 12.0 Hz, 2H), 7.48−
7.40 (m, 2H), 7.36−7.32 (m, 1H), 7.21−7.16 (m, 8H), 7.14−6.98
(m, 1H), 2.34 (s, 6H). 31P{1H} NMR (CDCl3, 162 MHz): δ −15.90.
MS (ESI) m/z: [M + H]+ Calcd for C24H22P+ 341; Found 341. IR
(film): 3079, 1567, 1473, 1432, 1393, 1080, 1026, 745, 698, 502
cm−1.
4-(Diphenylphosphanyl)benzaldehyde (39). According to the
general procedure B, reaction with p-methylbenzoyldiphenylphos-
phine 1a (61 mg, 0.20 mmol, 1.0 equiv), 4-bromobenzaldehyde (38.9
mg, 0.21 mmol, 1.05 equiv), toluene (0.5 mL), Cs2CO3 (71.7 mg,
0.22 mmol, 1.1 equiv), Pd2(dba)3 (4.6 mg, 0.005 mmol, 2.5 mol %),
and dppf (5.6 mg, 0.01 mmol, 5 mol %) afforded 39 (49.9 mg) in a
yield of 86% as a white amorphous solid. According to the general
procedure B, reaction with (diphenylphosphine)trihydroboron 38
1
EtOAc. H NMR (CDCl3, 400 MHz): δ 7.65−7.63 (m, 1H), 7.39−
7.27 (m, 11H), 7.00−6.93 (m, 2H), 6.37 (br s, 1H), 1.48 (s, 9H).
13C{1H} NMR (CDCl3, 101 MHz): δ 152.6, 138.6 (d, J = 8.3 Hz),
138.1 (d, J = 11.5 Hz), 137.0 (d, J = 11.0 Hz), 133.8 (d, J = 19.6 Hz),
129.3 (d, J = 7.2 Hz), 128.8, 128.5 (d, J = 6.9 Hz), 128.3 (d, J = 18.5
Hz), 123.4 (br d, J = 21.5 Hz), 119.1, 80.6, 28.3. 31P{1H} NMR
8993
J. Org. Chem. 2021, 86, 8987−8996