R. Shinohara et al. / Tetrahedron 75 (2019) 2717e2725
2723
EtOAc 1:1). The 1H and 13C NMR spectra were consistent with those
of the above racemic compound.
242 Hz); HRMS (EIþ): m/z calcd for C21H19F [Mþ] 290.1471, found
290.1472.
4.3.4. Butane-1,1,2-triyltribenzene (8c)
4.3.8. (2-(4-Chlorophenyl)propane-1,1-diyl)dibenzene (8h)
According to the general procedure for the substitution, phos-
phate 7c (53 mg, 0.195 mmol) in THF (1 mL) was added to a mixture
of Ph2CH2 (110 mg, 0.654 mmol) and n-BuLi (1.60 M in hexane, 0.37
mL, 0.59 mmol) in THF (1 mL) at e15 ꢀC and the solution was stirred
at e15 ꢀC for 15 min to afford 8c (44 mg, 79% yield) and Ph2CHEt
(11) (4 mg, 10%). Product 8c: solids; mp 76e77 ꢀC; IR (nujol) 1599,
According to the general procedure for the substitution, phos-
phate 7h (58 mg, 0.20 mmol) in THF (1 mL) was added to a mixture
of Ph2CH2 (109 mg, 0.644 mmol) and n-BuLi (1.60 M in hexane, 0.37
mL, 0.59 mmol) in THF (1 mL) at e15 ꢀC and the solution was stirred
at e15 ꢀC for 15 min to furnish 8h (54 mg, 89% yield): solids; mp
93e94 ꢀC; Rf 0.85 (hexane/EtOAc 1:1); IR (nujol) 1596, 1491, 1093,
1584, 1493, 751, 699 cme1; 1H NMR (400 MHz, CDCl3)
d
0.66 (t, J ¼
1011, 745, 694 cme1; 1H NMR (400 MHz, CDCl3)
d
1.16 (d, J ¼ 6.8 Hz,
7.4 Hz, 3 H), 1.46 (ddq, J ¼ 13.8, 11.4, 7.4 Hz, 1 H), 1.70 (ddq, J ¼ 13.8,
3.2, 7.4 Hz, 1 H), 3.32 (dt, J ¼ 3.2, 11.4 Hz, 1 H), 4.12 (d, J ¼ 11.4 Hz, 1
H), 6.93 (tt, J ¼ 7.2, 1.6 Hz, 1 H), 7.01e7.07 (m, 3 H), 7.09e7.16 (m, 6
H), 7.15e7.22 (m, 1 H), 7.28e7.34 (m, 2 H), 7.38e7.43 (m, 2 H);
3 H), 3.56 (dq, J ¼ 11.4, 6.8 Hz, 1 H), 3.99 (d, J ¼ 11.4 Hz, 1 H), 6.97 (tt,
J ¼ 6.8,1.6 Hz,1 H), 7.03e7.13 (m, 8 H), 7.18 (t, J ¼ 7.4 Hz,1 H), 7.30 (d,
J ¼ 7.8 Hz, 2 H), 7.37 (d, J ¼ 7.4 Hz, 2 H); 13C NMR (100 MHz, CDCl3)
d
22.1 (þ), 43.9 (þ), 59.4 (þ), 125.9 (þ), 126.4 (þ), 128.17 (þ), 128.21
13CeAPT NMR (100 MHz, CDCl3)
d
12.1 (þ), 27.9 (e), 52.0 (þ), 58.6
(þ), 128.24 (þ), 128.29 (þ), 128.7 (þ), 129.0 (þ), 131.4 (e), 143.6 (e),
143.9 (e), 144.5 (e); HRMS (EIþ): m/z calcd for C21H19Cl [Mþ]
306.1175, found 306.1181.
(þ), 125.6 (þ), 125.8 (þ), 126.3 (þ), 127.95 (þ), 128.00 (þ), 128.2 (þ),
128.3 (þ), 128.6 (þ), 128.7 (þ), 143.4 (e), 144.0 (e), 144.4 (e); HRMS
(EIþ): m/z calcd for C22H22 [Mþ] 286.1722, found 286.1723. The 1H
NMR spectrum of 11 was consistent with the literature data [2].
4.3.9. (2-(4-Bromophenyl)propane-1,1-diyl)dibenzene (8i)
4.3.5. (S)-Butane-1,1,2-triyltribenzene [(S)-8c]
According to the general procedure for the substitution, phos-
phate 7i (46 mg, 0.137 mmol) in THF (1 mL) was added to a mixture
of Ph2CH2 (74 mg, 0.44 mmol) and n-BuLi (1.63 M in hexane, 0.250
mL, 0.408 mmol) in THF (1 mL) at e15 ꢀC and the solution was
stirred at e15 ꢀC for 15 min to give 8i (38 mg, 79% yield): solids; mp
94e95 ꢀC; Rf 0.90 (hexane/EtOAc 2:1); IR (nujol) 1489, 1071, 1007,
According to the general procedure for the substitution,
diphenyl phosphate (S)-7d (86% ee, 195 mg, 0.529 mmol) in THF (1
mL) was added to a mixture of Ph2CH2 (0.281 mL,1.69 mmol) and n-
BuLi (1.55 M in hexane, 1.06 mL, 1.64 mmol) in THF (4 mL) at e15 ꢀC
and the solution was warmed to 0 ꢀC over 30 min to afford (S)-8c
(131 mg, 86%): 86% ee by HPLC (Chiralcel OJ-H, hexane/i-PrOH ¼
701 cme1; 1H NMR (400 MHz, CDCl3)
d
1.15 (d, J ¼ 6.8 Hz, 3 H), 3.55
99.5/0.5, 1.0 mL/min, 35 ꢀC, tR/min ¼ 12.7 (S-isomer, major), 19.3 (R-
(dq, J ¼ 11.4, 6.8 Hz, 1 H), 3.99 (d, J ¼ 11.4 Hz, 1 H), 6.94e7.02 (m, 3
H), 7.03e7.12 (m, 4 H), 7.17 (t, J ¼ 7.8 Hz,1 H), 7.25 (d, J ¼ 8.3 Hz, 2 H),
7.29 (t, J ¼ 7.5 Hz, 2 H), 7.37 (d, J ¼ 8.0 Hz, 2 H); 13C NMR (100 MHz,
21
isomer, minor)); solids; mp 87e88 ꢀC; Rf 0.30 (hexane only); [
a
]
364
21
21
21
21
e22, [
a
]
þ0, [
a
]
þ6 (c 0.89, CHCl3); [
a
]
e51, [
a]
e19 (c
þ4.0 (c 2.2,
436
546
364
436
21
21
21
0.94, EtOH); lit [11]. [
a
]
e21.8, [
a]
þ0, [
a]
CDCl3)
d
22.1 (þ), 43.9 (þ), 59.3 (þ), 119.5 (e), 125.9 (þ), 126.4 (þ),
364
21
436
546
21
CHCl3); [
a]
e65.7, [
a
]
436 e25.2 (c 1, EtOH).
128.15 (þ), 128.22 (þ), 128.7 (þ), 129.4 (þ), 131.2 (þ), 143.5 (e),
143.8 (e), 145.0 (e); HRMS (EIþ): m/z calcd for C21H19Br [Mþ]
350.0670, found 350.0674.
364
4.3.6. (3-Methylbutane-1,1,2-triyl)tribenzene (8e)
According to the general procedure for the substitution,
diphenyl phosphate 7f (76 mg, 0.199 mmol) in THF (1 mL) was
added to a mixture of Ph2CH2 (117 mg, 0.695 mmol) and n-BuLi
(1.60 M in hexane, 0.37 mL, 0.59 mmol) in THF (1 mL) at e15 ꢀC, and
the solution was stirred at e15 ꢀC for 15 min to afford 8e (56 mg,
94% yield): solids; mp 114e115 ꢀC; Rf 0.90 (hexane/EtOAc 2:1); IR
(nujol) 1598, 1071, 1031, 741, 700 cme1; 1H NMR (300 MHz, CDCl3)
4.3.10. 4-(1,1-Diphenylpropan-2-yl)benzonitrile (8j)
According to the general procedure for the substitution, phos-
phate 7j (56 mg, 0.20 mmol) in THF (1 mL) was added to a mixture
of Ph2CH2 (112 mg, 0.666 mmol) and n-BuLi (1.60 M in hexane, 0.37
mL, 0.59 mmol) in THF (1 mL) at e15 ꢀC and the mixture was stirred
at e15 ꢀC for 15 min to afford 8j (51 mg, 86% yield): liquid; Rf 0.87
(hexane/EtOAc 1:1); IR (neat) 2226, 1606, 1494, 1451, 704 cme1; 1H
d
0.72 (d, J ¼ 6.9 Hz, 3 H), 0.79 (d, J ¼ 6.9 Hz, 3 H), 1.83 (d of sept., J ¼
3.0, 6.9 Hz, 1 H), 3.55 (dd, J ¼ 12.3, 3.0 Hz, 1 H), 4.44 (d, J ¼ 12.3 Hz, 1
H), 6.89 (tt, J ¼ 7.2, 1.2 Hz, 1 H), 6.98e7.22 (m, 10 H), 7.29 (t, J ¼ 7.8
NMR (300 MHz, CDCl3)
d
1.19 (d, J ¼ 6.6 Hz, 3 H), 3.64 (dq, J ¼ 11.5,
6.6 Hz, 1 H), 4.01 (d, J ¼ 11.5 Hz, 1 H), 6.94e7.46 (m, 14 H); 13C NMR
Hz, 2 H), 7.42 (d, J ¼ 8.1 Hz, 2 H); 13C NMR (75 MHz, CDCl3)
d 15.9
(75 MHz, CDCl3)
d
21.7 (þ), 44.7 (þ), 59.1 (þ), 109.6 (e), 119.1 (e),
(þ), 22.6 (þ), 28.5 (þ), 54.1 (þ), 54.7 (þ), 125.6 (þ), 125.8 (þ), 126.3
(þ), 127.3 (þ), 128.0 (þ), 128.1 (þ), 128.4 (þ), 128.8 (þ), 130.3 (þ),
139.3 (e), 144.1 (e), 144.7 (e); HRMS (EIþ): m/z calcd for C23H24
[Mþ] 300.1878, found 300.1875.
126.1 (þ), 126.6 (þ), 128.0 (þ), 128.1 (þ), 128.3 (þ), 128.5 (þ), 128.8
(þ), 132.0 (þ), 143.0 (e), 143.2 (e), 151.7 (e); HRMS (EIþ): m/z calcd
for C22H19N [Mþ] 297.1517, found 297.1515.
4.3.7. (2-(4-Fluorophenyl)propane-1,1-diyl)dibenzene (8g)
4.3.11. (2-(p-Tolyl)propane-1,1-diyl)dibenzene (8k)
According to the general procedure for the substitution, phos-
phate 7g (55 mg, 0.20 mmol) in THF (1 mL) was added to a mixture
of Ph2CH2 (110 mg, 0.654 mmol) and n-BuLi (1.60 M in hexane, 0.37
mL, 0.59 mmol) in THF (1 mL) at e15 ꢀC and the solution was stirred
at e15 ꢀC for 15 min to give 8g (52 mg, 91% yield): solids; mp 76e78
ꢀC; Rf 0.92 (hexane/EtOAc 1:1); IR (nujol) 1597, 1509, 1221, 833, 700
According to the general procedure for the substitution, phos-
phate 7k (52 mg, 0.19 mmol) in THF (1 mL) was added to a mixture
of Ph2CH2 (108 mg, 0.64 mmol) and n-BuLi (1.60 M in hexane, 0.36
mL, 0.58 mmol) in THF (1 mL) at e15 ꢀC and the solution was stirred
at e15 ꢀC for 15 min to give 8k (47 mg, 86% yield): solids; mp 52e54
ꢀC; Rf 0.88 (hexane/EtOAc 2:1); IR (nujol) 1596, 1513, 1491, 1071, 810
cme1; 1H NMR (400 MHz, CDCl3)
d
1.17 (d, J ¼ 6.8 Hz, 3 H), 3.57 (dq,
cme1; 1H NMR (400 MHz, CDCl3)
d
1.16 (dd, J ¼ 6.9, 2.0 Hz, 3 H), 2.19
J ¼ 11.4, 6.8 Hz,1 H), 3.98 (d, J ¼ 11.4 Hz,1 H), 6.82 (t, J ¼ 8.0 Hz, 2 H),
6.96 (t, J ¼ 6.5 Hz, 1 H), 7.02e7.12 (m, 6 H), 7.18 (t, J ¼ 7.8 Hz, 1 H),
7.29 (t, J ¼ 7.1 Hz, 2 H), 7.38 (d, J ¼ 7.7 Hz, 2 H); 13C NMR (100 MHz,
(s, 3 H), 3.49e3.60 (m, 1 H), 4.04 (d, J ¼ 11.4 Hz, 1 H), 6.90e7.19 (m,
10 H), 7.27 (dt, J ¼ 1.5, 7.4 Hz, 2 H), 7.37 (t, J ¼ 7.9 Hz, 2 H); 13C NMR
(100 MHz, CDCl3)
d
21.0 (þ), 22.4 (þ), 43.9 (þ), 59.4 (þ), 125.7 (þ),
CDCl3)
d
22.2 (þ), 43.7 (þ), 59.8 (þ), 114.9 (þ) (d, J ¼ 21 Hz), 125.9
126.3 (þ), 127.5 (þ), 128.1 (þ), 128.28 (þ), 128.32 (þ), 128.6 (þ),
128.9 (þ), 135.1 (e), 142.9 (e), 144.1 (e), 144.4 (e); HRMS (EIþ): m/z
calcd for C22H22 [Mþ] 286.1722, found 286.1724.
(þ),126.4 (þ), 128.15 (þ),128.21 (þ),128.27 (þ),128.7 (þ),129.0 (þ)
(d, J ¼ 8 Hz), 141.6 (e) (d, J ¼ 3 Hz), 143.7 (e), 144.0 (e), 161.0 (d, J ¼