Y. Murata, N. Kakusawa, Y. Arakawa et al.
Journal of Organometallic Chemistry 928 (2020) 121545
ꢀ
formation using other coupling partners in the presence of the cat-
alytic system, are under investigation.
4.3.2. (E)-4-(4 -Methoxylphenyl)-3-buten-2-one (10) [33]
Colorless plate (167 mg, 95%), m.p. 70–72 °C (from Hexane,
Lit. 72–74 °C). 1H NMR (400 MHz, CDCl ): δ 7.52–7.46 (m, 3H,
3
4
. Experimental
Ar-H+CH=CHCO), 6.92 (dt, 2H, J = 9.6, 2.8 Hz, Ar-H), 6.61 (d,
1
H, J = 16.8 Hz, ArCH=CH), 3.85 (s, 3H, CH ), 2.37 (s, 3H, CH ).
3
3
1
3
4
.1. General
C NMR (100 MHz, CDCl ): δ 198.5 (C), 161.7 (C), 143.4 (CH),
3
1
30.1 (CH), 127.1 (C), 125.1 (CH), 114.5 (CH), 55.5 (CH ), 27.5
3
Melting points were measured on a Yanagimoto micro melting
(CH ). FTIR (KBr): 2941, 1681, 1626, 1465, 1392, 1290, 1172, 989,
3
point hot stage apparatus and are uncorrected. 1H NMR (CHCl : δ:
667 cm . LRMS (EI): m/z 177.1 ([M+H] , 75), 161.1 (100), 133.1
−1
+
3
+
7
.26 ppm as an internal standard), 13C NMR (CDCl : δ: 77.00 ppm
(40), 115.1 (16). HRMS: m/z [M] calcd for C
H
11 12
O : 176.0837.
3
2
as an internal standard) and 19 F NMR (PhCF : δ: -64.0 ppm as an
Found: 176.0840.
3
external standard) spectra were recorded on JEOL ECZ-400S spec-
ꢀ
trometer (400 MHz, 100 MHz and 376 MHz) in CDCl . IR spec-
4.3.3. (E)-4-(4 -Methylphenyl)-3-buten-2-one (11) [32]
3
tra were recorded on a Shimadzu FTIR-8400S spectrophotometer
and reported in terms of frequency of absorption (cm 1). Only se-
lected IR bands are reported. Mass spectra were obtained on a JEOL
JMP-DX300 instrument (70 eV, 300 mA). Column chromatography
was performed on Silica Gel 60 N (Kanto Chemical Co., Inc.). Each
reagent was purchased from Wako Pure Chemical Industries, Ltd.
Japan, Tokyo Kasei Kogyo Co., LTD and SIGMA-ALDRICH Japan K.K.
and used without further purification.
Pale yellow oil (141 mg, 88%). 1H NMR (400 MHz, CDCl ): δ
3
−
7.48 (d, 1H, J = 16.0 Hz, CH=CHCO), 7.43 (d, 2H, J = 8.4 Hz, Ar-H),
7.19 (d, 2H, J = 8.4 Hz, Ar-H), 6.67 (d, 1H, J = 16.0 Hz, ArCH=CH),
13
2.37 (s, 3H, CH ), 2.36 (s, 3H, CH ). C NMR (100 MHz, CDCl ): δ
3
3
3
198.7 (C), 143.6 (CH), 141.1 (C), 131.7 (C), 129.8 (CH), 128.4 (CH),
126.3 (CH), 27.5 (CH ), 21.6 (CH ). FTIR (neat): 2941, 1681, 1626,
1423, 1359, 1249, 1172, 989, 667 cm 1. LRMS (EI): m/z 160.1 ([M] ,
3
3
−
+
+
13), 145.1 (100), 115.1 (49), 91.1 (20). HRMS: m/z [M] calcd for
C11 H12O: 160.0888. Found: 160.0890.
4
.2. Preparation of t-butyl-12-aryl-5,6,7,12-tetrahydrodibenzo[c,f]
ꢀ
[1,5]azastibocines
4.3.4. (E)-4-(4 -Chlorophenyl)-3-buten-2-one (12) [33]
Colorless needle (148 mg, 82%), m.p. 57–59 °C (from Hexane,
Azastibocines were prepared according to the literature and the
Lit. 59–60 °C). 1H NMR (400 MHz, CDCl ): δ 7.49–7.44 (m, 3H, Ar-
3
spectroscopic data of known compounds are in accordance with
H+CH=CHCO), 7.37 (dt, 2H, J = 8.8, 2.4 Hz, Ar-H), 6.68 (d, 1H,
13
the literature [13]. 1a; m.p. 130–133 °C (Lit. 134–135 °C), 1b; m.p.
J = 16.4 Hz, ArCH=CH), 2.38 (s, 3H, CH ). C NMR (100 MHz,
3
136–138 °C (Lit. 142–143 °C), 1c; m.p. 179–180.5 °C (Lit. 183–
CDCl ): δ 198.3 (C), 142.1 (CH), 136.6 (C), 133.1 (C), 129.6 (CH),
3
184 °C), 1d; m.p. 140–142 °C (Lit. 148–149 °C)
129.4 (CH), 127.6 (CH), 27.9 (CH ). FTIR (KBr): 2970, 1660, 1626,
3
1
419, 1361, 1298, 1180, 977, 684 cm 1. LRMS (EI): m/z 180.0 ([M] ,
− +
+
4
.2.1. t-Butyl-12-p-trifluoromethylphenyl-5,6,7,12-
27), 165.0 (100), 137.0 (48), 102.1 (58). HRMS: m/z [M] calcd for
tetrahydrodibenzo[c,f][1,5]azastibocine (1e)
C10H ClO: 180.0342. Found: 180.0339.
9
Colorless prism, m.p. 174–176 °C (from CH Cl /Hexane). 1H
4.3.5. (E)-4-(4 -Trifluoromethylphenyl)-3-buten-2-one (13) [33]
ꢀ
2
2
NMR (400 MHz, CDCl ): δ 7.81 (d, 2H, J = 7.8 Hz, Ar-H), 7.64 (d,
Colorless plate (152 mg, 71%), m.p. 60–62 °C (from MeOH, Lit.
3
2
H, J = 7.8 Hz, Ar-H), 7.19 (td, 2H, J = 7.3, 1.4 Hz, Ar-H), 7.10–
.03 (m, 6H, Ar-H), 4.20 (d, 2H, J = 15.6 Hz, CH ), 4.18 (d, 2H,
60–61 °C). 1H NMR (400 MHz, CDCl ): δ 7.65 (s, 4H, Ar-H), 7.52 (d,
3
7
1H, J = 16.4 Hz, CH=CHCO), 6.78 (d, 1H, J = 16.4 Hz, ArCH=CH),
2
1
3
13
J = 15.6 Hz, CH ) 1.25 (s, 9H, CH ). C NMR (100 MHz, CDCl ):
2.41 (s, 3H, CH ). C NMR (100 MHz, CDCl ): δ 198.1 (C), 141.5
2
3
3
3
3
δ 152.4 (C), 146.7 (C),139.1 (CH), 136.02 (CH), 135.92 (C), 130.0 (C,
(CH), 138.0 (C), 132.1 (C, q, 2JC,F = 33 Hz), 129.3 (CH), 128.5 (CH),
C,F
q, 2JC,F = 31 Hz), 128.1 (CH), 127.3 (CH), 126.3 (CH), 124.61 (CH, q,
126.1 (C, q, 3JC,F = 3.8 Hz), 123.9 (C, q,
1
J
= 271 Hz), 27.9
3JC,F = 3.9 Hz), 124.59 (C, q,
1
J
= 272 Hz), 57.8 (C), 54.8 (CH ),
(CH ). FTIR (KBr): 2934, 1664, 1614, 1415, 1329, 1259, 1168, 979,
3
C,F
2
19
−1
+
2
6.9 (CH ). F NMR (376 MHz, CDCl ): δ -63.7. LRMS (EI): m/z
758 cm . LRMS (EI): m/z 215.1 ([M+H] , 21), 199.0 (100), 171.0
3
+
3
+
+
5
17.1 ([M] , 5), 446.0 (5), 372.0 ([M-(C H CF )] , 100), 316.0 (45).
(53), 151.0 (73). HRMS: m/z [M] calcd for C H F O: 214.0605.
6
4
3
11
9 3
+
HRMS: m/z [M] calcd for C25H25F3NSb: 517.0977. Found: 517.0974.
Found: 214.0608.
4
.3. General procedure for the Heck reaction with azastibocines
4.3.6. (E)-1-Phenyl-1-penten-3-one (14) [34]
Pale yellow oil (144 mg, 90%). 1H NMR (400 MHz, CDCl ): δ
3
A mixture of azastibocine (1.0 mmol), alkene (3.0 mmol, 3 eq.)
7.58–7.54 (m, 3H, Ar-H+CH=CHCO), 7.41–7.39 (m, 3H, Ar-H), 6.75
and PdCl2 (18 mg, 0.1 mmol, 10 mol%) in DMA (3.0 mL) was stirred
at 80 °C under air. The completion of the reaction was moni-
tored using TLC. After being completed, the reaction mixture was
cooled to room temperature and purified by chromatography (17:
n-Hexane, 3, 14: n-Hexane:CH Cl = 5:1, 10–13, 15, 18–22, 25: n-
(d, 1H, J = 16.4 Hz, ArCH=CH), 2.71 (q, 2H, J = 7.2 Hz, CH ), 1.17
2
1
3
(t, 3H, J = 7.6 Hz, CH ). C NMR (100 MHz, CDCl ): δ 201.2 (C),
3
3
142.4 (CH), 134.8 (C), 130.5 (CH), 129.1 (CH), 128.4 (CH), 126.2
(CH), 34.2 (CH ), 8.41 (CH ). FTIR (neat): 2976, 1666, 1610, 1458,
2
3
1375, 1188, 977, 690 cm 1. LRMS (EI): m/z 160.1 ([M] , 26), 131.1
−
+
2
2
+
Hexane:EtOAc = 5:1, 24: n-Hexane:EtOAc = 2:3) to give the Heak
(100), 103.1 (57), 77.1 (29). HRMS: m/z [M] calcd for C11 H12O:
reaction product.
160.0888. Found: 160.0887.
4
.3.1. Benzylideneacetone (3) [32]
Colorless oil (136 mg, 94%). 1H NMR (400 MHz, CDCl ): δ 7.56–
4.3.7. (E)-1-Phenyl-1-octen-3-one (15) [34]
Pale yellow oil (138 mg, 68%). 1H NMR (400 MHz, CDCl ): δ
3
3
7
.54 (m, 2H, Ar-H), 7.50 (d, 1H, J = 16.0 Hz, CH=CHCO), 7.41–7.39
7.57–7.53 (m, 3H, Ar-H+CH=CHCO), 7.40–7.39 (m, 3H, Ar-H,), 6.75
(
m, 3H, Ar-H), 6.73 (d, 1H, J = 16.5 Hz, ArCH=CH), 2.38 (s, 3H,
(d, 1H, J = 16.4 Hz, ArCH=CH), 2.66 (t, 2H, J = 7.2 Hz, CH ), 1.72–
2
13
CH ). C NMR (100 MHz, CDCl ): δ 198.4 (C), 143.4 (CH), 134.4
1.67 (m, 2H, CH ), 1.36–1.33 (m, 4H, CH ), 0.91 (t, 3H, J = 6.8 Hz,
3
3
2
2
13
(
(
C), 130.5 (CH), 128.9 (CH), 128.2 (CH), 127.1 (CH), 27.5 (CH ). FTIR
neat): 3003, 1681, 1654, 1452, 1361, 1257, 1176, 985, 669 cm 1.
CH ). C NMR (100 MHz, CDCl ): δ 201.9 (C), 142.5 (CH), 134.8
3 3
3
−
(C), 130.6 (CH), 129.1 (CH), 128.4 (CH), 126.4 (CH), 41.1 (CH ), 31.7
2
+
LRMS (EI): m/z 145.1 ([M-H] , 75), 131.1 (100), 103.1 (95), 77.1 (50).
(CH ), 24.3 (CH ), 22.7 (CH ), 14.2 (CH ). FTIR (neat): 2928, 1664,
2 2 2 3
+
−1 +
HRMS: m/z [M] calcd for C10H10O: 146.0732. Found: 146.0734.
1647, 1450, 1371, 1178, 981, 688 cm . LRMS (EI): m/z 202.1 ([M] ,
5