Direct C-H bond arylation of fluorenes with aryl chlorides catalyzed by N-heterocyclic carbene-palladium(ii)-1-methylimidazole complex and further transformation of the products in a one-pot procedure

Article abstract of DOI:10.1039/c4ob01594k

We report here the NHC-Pd(ii)-Im complex 1-catalyzed direct C-H bond functionalization of the C9 position of fluorenes with aryl chlorides and further transformation of the resulting products in a one-pot procedure. Under the optimal conditions, arylated fluorenes can be obtained in moderate to almost quantitative yields using various activated and unactivated (hetero)aryl chlorides as the arylating reagents. Furthermore, if the mixture from the arylation reaction is exposed to air, the C9-oxidized products can be obtained in acceptable to good yields in a one-pot procedure. In addition, alkyl groups can also be efficiently introduced to the above mixture from the arylation reaction, producing further C9-alkylated products in good to almost quantitative yields in a one-pot procedure, thus providing an expedient, inexpensive and practical strategy for the mono- and di-functionalization of fluorenes. This journal is

Full text of DOI:10.1039/c4ob01594k

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Direct C–H bond arylation of fluorenes with aryl
chlorides catalyzed by N-heterocyclic carbene–
palladium(II)–1-methylimidazole complex and
further transformation of the products in a one-
pot procedure†
Cite this: Org. Biomol. Chem., 2014,
12, 8488
Ya-Yun Ji,a Li-Li Lu,‡a Yu-Chun Shi‡a and Li-Xiong Shao*a,b
We report here the NHC–Pd(II)–Im complex 1-catalyzed direct C–H bond functionalization of the C9
position of fluorenes with aryl chlorides and further transformation of the resulting products in a one-pot
procedure. Under the optimal conditions, arylated fluorenes can be obtained in moderate to almost
quantitative yields using various activated and unactivated (hetero)aryl chlorides as the arylating reagents.
Furthermore, if the mixture from the arylation reaction is exposed to air, the C9-oxidized products can be
obtained in acceptable to good yields in a one-pot procedure. In addition, alkyl groups can also be
efficiently introduced to the above mixture from the arylation reaction, producing further C9-alkylated
products in good to almost quantitative yields in a one-pot procedure, thus providing an expedient, in-
expensive and practical strategy for the mono- and di-functionalization of fluorenes.
Received 27th July 2014,
Accepted 27th August 2014
DOI: 10.1039/c4ob01594k
www.rsc.org/obc
and have found that it showed efficient catalytic activity toward
traditional C–C and C–N coupling reactions using easily avail-
Introduction
The direct C–H bond functionalization reactions, which at able and cost-effective aryl chlorides as the substrates under
least can avoid additional pre-functionalization of one of the suitable conditions.4 In addition, very recently, we found that
reaction partners, have been an expedient, economical, and the NHC–Pd(II)–Im complex 1 was also a good catalyst for the
beneficial alternative to the traditional coupling reactions direct C–H bond arylation of (benz)oxazoles and (benz)imida-
between organic electrophiles and organometallic nucleo- zoles using aryl chlorides as the arylating reagents.5 These
philes.1 During the past decade, in contrast to the abundant results thus prompted us to further investigate its application
applications of N-heterocyclic carbene (NHC)-metal complex- toward other direct C–H bond arylation reactions using aryl
catalyzed traditional coupling reactions,2 only slight attention chlorides as the arylating reagents. In this case, fluorenes were
was paid to their applications toward direct C–H bond functio- chosen as the other partners, because functionalized fluorenes
nalizations,3 indicating that much room still remains in this are very important moieties for various organic materials.6 In
field using NHC–metal complexes as the catalysts.
2012 and 2013, Wu et al.7 and Song, Xie and Huang et al.8
Recently, from easily available starting materials such as have independently reported the Pd-catalyzed direct C–H bond
the imidazolium salt [1,3-bis(2,6-diisopropylphenyl)imidazo- arylation of the C9 position of fluorenes in the presence of
lium chloride, IPr·HCl], PdCl2 and 1-methylimidazole, we have phosphine ligands. However, in most cases, only aryl bromides
developed
a N-heterocyclic carbene–palladium(II)–1-methyl- can be used as the coupling partners. For instance, only very
imidazole [NHC–Pd(II)–Im] complex 1 under mild conditions, few examples involving aryl chlorides were reported,7 implying
that great challenges still remain in using the less active, while
cheaper and more easily available aryl chlorides as the arylating
reagents in such a transformation. One may draw the conclusion
that efficient direct C–H bond arylation of fluorenes with aryl
chlorides has been far from well investigated to date. Here, we
reported the first example of phosphine-free, NHC–Pd(II)–Im
complex 1-catalyzed direct C–H bond arylation of fluorenes at
the C9 position with various aryl chlorides and further
functionalization of the products in a one-pot procedure.
aCollege of Chemistry and Materials Engineering, Wenzhou University, Chashan
University Town, Wenzhou, Zhejiang Province 325035, People’s Republic of China.
E-mail: Shaolix@wzu.edu.cn; Fax: +86 57786689300; Tel: +86 57786689300
bCollege of Chemistry and Life Sciences, Zhejiang Normal University, Jinhua,
Zhejiang Province 321004, People’s Republic of China
†Electronic supplementary information (ESI) available: Copy of 1H and 13C NMR
spectra of compounds 4, 5 and 7. See DOI: 10.1039/c4ob01594k
‡These two authors contributed equally.
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Table 2 NHC–Pd(II)–Im complex
fluorene 2a and aryl chlorides 3
1
catalyzed reactions between
Results and discussion
We began our investigation by using fluorene 2a (1.0 mmol)
and chlorobenzene 3a (0.75 mmol) as model substrates in the
presence of NHC–Pd(II)–Im complex 1 (1.0 mol%) at 120 °C for
12 h for the optimization of the reaction conditions. It was
found that both the solvent and the base played important
roles in this reaction. For example, in the first round, dioxane
was chosen as solvent, and KOtBu showed the best result,
giving the desired arylated product 4a in 99% yield (Table 1,
entry 1).9 However, in the presence of other bases such as
NaOtBu, KOH, NaOH, Na2CO3, Cs2CO3 and K2CO3, no desired
product was detected (Table 1, entries 2–7). In the second
round, solvent screening showed that dioxane was the best,
surpassing THF (82%) and toluene (73%) (Table 1, entries 8
and 9). In addition, no product was observed when using
CH3CN as solvent in the reaction (Table 1, entry 10).
With the optimal conditions established (Table 1, entry 1),
the reaction was then first tested by the treatment of fluorene
2a with a variety of aryl chlorides 3 (Table 2). All reactions pro-
ceeded smoothly to give the desired C–H bond arylated pro-
ducts 4 in moderate to almost quantitative yields. As can be
seen from Table 2, the substituents on the aryl chlorides 3 did
not affect the reactions significantly in most cases. For
example, when electron-rich substituents, such as methoxy,
methyl and dimethylamino groups, or electron-poor groups,
such as fluorine atoms, were attached to the phenyl rings of
aryl chlorides 3, respectively, all reactions proceeded well
Entrya
3 (R′)
Yieldb (%)
1
2
3
4
5
6
7
8
3b (2-OMe)
3c (3-OMe)
3d (4-OMe)
3e (2-Me)
3f (3-Me)
3g (4-Me)
3h (2-F)
3i (3-F)
3j (4-F)
3k (2,6-Me2)
3l (4-NMe2)
4b, 94
4c, 96
4d, 94
4e, 99c
4f, 93
4g, 96
4h, 80
4i, 78
4j, 93
4k, 91
4l, 82
9
10
11
12
4m, 74
13
4n, 65
a All reactions were carried out using 2a (1.0 mmol), 3 (0.75 mmol),
1 (1.0 mol%), KOtBu (1.5 equiv.) in dioxane (2.0 mL) at 120 °C for 12 h.
b Isolated yields. c The ratio (syn/anti = 63/37) was determined by 1H
NMR.
enough (Table 2, entries 1–11). Sterically hindering substitu-
ents, such as 2-methoxy, 2-methyl, 2-fluoro and even 2,6-
dimethyl groups attached to the phenyl rings of aryl chlorides 3,
were all tolerated to give the expected products 4b, 4e, 4h and
4k in good to almost quantitative yields, respectively (Table 2,
entries 1, 4, 7 and 10). In addition, heteroaryl chlorides such as
2-chloropyridine 3m and 3-chloropyridine 3n were also good
substrates, giving the arylated products 4m and 4n in satisfac-
tory yields, respectively (Table 2, entries 12 and 13).
Table 1 Optimization for the reaction conditions
Encouraged by these results, the reactions of various other
fluorenes 2 and aryl chlorides 3 were further investigated
under the optimal conditions. As can be seen from Table 3, all
reactions can give the desired arylated products 4 in good to
almost quantitative yields, regardless of whether electron-rich
or -poor or sterically hindering substituents were attached on
the phenyl rings of either substrate. For instance, aryl chlor-
ides possessing sterically hindering substituents reacted very
well to give the corresponding products 4p and 4ac in good to
almost quantitative yields (Table 3, entries 2 and 15).
It seems that products 4 are liable to be oxidized if the reac-
tion mixture is exposed to air. For example, when the reactions
between fluorenes 2 and aryl chlorides 3 were finished and
then the mixture was exposed to air at room temperature for
another 1 h, 9-aryl-9-hydroxyfluorenes 5 can be obtained in
acceptable to good yields (Table 4). Therefore, once the C–H
bond arylation reaction is completed, the work-up should be
carried out as soon as possible in order to achieve satisfactory
Entrya
Solvent
Base
Yieldb (%)
1
2
3
4
5
6
7
8
9
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
THF
KOtBu
NaOtBu
KOH
NaOH
Na2CO3
Cs2CO3
K2CO3
KOtBu
KOtBu
KOtBu
99
ND
ND
ND
ND
ND
ND
82
Toluene
CH3CN
73
ND
10
a All reactions were carried out using 2a (1.0 mmol), 3a (0.75 mmol),
1 (1.0 mol%), base (1.5 equiv.) in solvent (2.0 mL) at 120 °C for 12 h.
b Isolated yields. ND = not detected.
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yields of products 4. As can be seen from Table 4, it seems that
the substituents on the fluorenes 2 and aryl chlorides 3 did
not affect the reactions significantly. For instance, aryl chlor-
ides 3 having electron-rich, -neutral or -poor groups or steri-
cally hindering substituents were all tolerated to give the
corresponding products 5 in moderate to good yields. The
reaction of a heteroaryl chloride such as 3-chloropyridine 3n
also proceeded smoothly in a one-pot procedure, giving
product 5i in an acceptable yield (Table 4, entry 9).
Since the normal direct C–H bond arylated products 4 are
liable to be oxidized once the reaction mixture is exposed to
air (Table 4), which may be partially due to the acidic hydrogen
on the C9 position, therefore we then turned our interest atten-
tion to the further functionalization of the acidic hydrogen of
products 4 by alkylation in a one-pot procedure. To our satis-
faction, when the amount of KOtBu was increased to 2.5 equiv.
in the first step of the arylation reaction under identical con-
Table 3 NHC–Pd(II)–Im complex
fluorenes 2 and aryl chlorides 3
1 catalyzed reactions between
Entrya
2 (R)
3 (R′)
Yieldb (%)
1
2
2b (2-Me)
2b
3a (H)
3b (2-OMe)
3d (4-OMe)
3f (3-Me)
3g (4-Me)
3j (4-F)
3l (4-NMe2)
3a
3d
3g
3j
3l
3c (3-OMe)
3d
3e (2-Me)
3g
3l
4o, 99
4p, 99
4q, 89
4r, 89
4s, 88
4t, 80
4u, 87
4v, 85
4w, 92
4x, 87
4y, 76
4z, 86
4aa, 92
4ab, 82
4ac, 83c
4ad, 83
4ae, 93
3
4
2b
2b
5
6
2b
2b
7
8
2b
2c (4-Me)
9
2c
2c
2c
2c
2d (2-F)
2d
2d
2d
10
11
12
13
14
15
16
17
Table 5 NHC–Pd(II)–Im complex 1 catalyzed reactions of fluorenes 2
with aryl chlorides 3 and further alkylation in a one-pot procedure
2d
a All reactions were carried out using 2 (1.0 mmol), 3 (0.75 mmol),
1 (1.0 mol%), KOtBu (1.5 equiv.) in dioxane (2.0 mL) at 120 °C for 12 h.
b Isolated yields. c The ratio (syn/anti = 64/36) was determined by 1H
NMR.
Entrya
2 (R)
3 (R′)
6 (R″/X)
Yieldb (%)
1
2
3
4
5
6
7
8
2a (H)
2a
2a
2a
2a
2a
2a
2a
2a
3a (H)
6a (benzyl/Cl)
6a
6a
6a
6a
6a
6a
6a
6b (Et/Br)
6c (allyl/Cl)
6d (Me/I)
6a
7a, 99
7b, 99
7c, 98
7d, 99
7e, 99
7f, 98
7g, 98
7h, 83
7i, 94c
7j, 93
7k, 94d
7l, 81
3c (3-OMe)
3d (4-OMe)
3f (3-Me)
3g (4-Me)
3i (3-F)
3j (4-F)
3l (4-NMe2)
3a
Table 4 NHC–Pd(II)–Im complex 1 catalyzed reactions of fluorenes 2
with aryl chlorides 3 and further oxidation in a one-pot procedure
9
10
11
12
2a
2a
2a
3a
3a
Entrya
2 (R)
3 (R′)
Yieldb (%)
13
2a
6a
7m, 89
1
2
3
4
5
6
7
8
2a (H)
2a
2a
2a
2a
2a
2a
2a
3a (H)
5a, 64
5b, 84
5c, 72
5d, 69
5e, 65
5f, 68
5g, 60
5h, 68
3b (2-OMe)
3c (3-OMe)
3d (4-OMe)
3g (4-Me)
3h (2-F)
3i (3-F)
3j (4-F)
14
15
16
17
18
19
20
21
22
23
24
25
2b (2-Me)
2b
2b
2b
2c (4-Me)
2c
2c
2c
2c
2d (2-F)
2d
2d
3a
3d
3g
3l
3a
3d
3g
3j
6a
6a
6a
6a
6a
6a
6a
6a
6a
6a
6a
6a
7n, 99
7o, 99
7p, 96
7q, 99
7r, 93
7s, 84
7t, 99
7u, 94
7v, 86
7w, 99
7x, 99
7y, 91
9
2a
5i, 53
3l
3a
3g
3l
10
11
12
13
2b (2-Me)
2b
2d (2-F)
3d
3g
3d
3g
5j, 75
5k, 75
5l, 69
5m, 70
a All reactions were carried out using 2 (1.0 mmol), 3 (0.75 mmol),
1 (1.0 mol%), KOtBu (2.5 equiv.) in dioxane (2.0 mL) at 120 °C for 12 h,
then 6 (1.0 mmol) was added and the mixture was stirred at rt for
another 6 h. b Isolated yields. c The ratio (syn/anti = 83/17) was
determined by 1H NMR. d The ratio (syn/anti = 87/13) was determined
by 1H NMR.
2d
a All reactions were carried out using 2 (1.0 mmol), 3 (0.75 mmol),
1 (1.0 mol%), KOtBu (1.5 equiv.) in dioxane (2.0 mL) at 120 °C for 12 h,
then the mixture was stirred at rt under air for another 1 h. b Isolated
yields.
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ditions, then alkyl scaffolds can be efficiently introduced, General procedure for the NHC–Pd(II)–Im complex-catalyzed
giving the final products 7 in good to almost quantitative reactions of fluorenes with aryl chlorides and further oxidation
yields (Table 5). It seems that better yields can be achieved in in a one-pot procedure
these two-step, one-pot procedures in most cases, which also
Under a N2 atmosphere, fluorenes 2 (1.0 mmol), NHC–Pd(II)–
indicates the instability of the arylated products 4 obtained
Im complex 1 (0.01 mmol), KOtBu (1.125 mmol), dioxane
from the first step.
(2.0 mL) and aryl chlorides 3 (0.75 mmol) were successively
added into a Schlenk reaction tube. The mixture was stirred
vigorously at 120 °C for 12 h, and then it was cooled to room
temperature and stirred for another 1 h under an atmosphere
Conclusions
of air. Then the solvent was removed under reduced pressure
and the residue was purified by flash column chromatography
(SiO2) (eluent: petroleum ether–ethyl acetate = 10 : 1) to obtain
In conclusion, the first example of phosphine ligand-free
direct C–H bond arylation of the C9 position of fluorenes
the pure product 5.
using various activated and unactivated (hetero)aryl chlorides
as the arylating reagents was achieved in the presence of a
well-defined, easily available NHC–Pd(II) complex.10 Under the
General procedure for the NHC–Pd(II)–Im complex-catalyzed
reactions of fluorenes with aryl chlorides and further
alkylation in a one-pot procedure
optimal conditions, various fluorenes and aryl chlorides can
react sufficiently to give the expected arylated products in good
to almost quantitative yields. Electron-rich, neutral, electron-
poor and sterically hindered substituents on both substrates
are tolerated. In addition, the arylated products can be further
oxidized or alkylated in a one-pot procedure to give di-functio-
nalized fluorenes in good to almost quantitative yields. The
methodology reported in this paper will become a beneficial
supplement to traditionally reported methods for the
functionalization of fluorenes in organic synthesis.
Under a N2 atmosphere, fluorenes 2 (1.0 mmol), NHC–Pd(II)–
Im complex 1 (0.01 mmol), KOtBu (1.875 mmol), dioxane
(2.0 mL) and aryl chlorides 3 (0.75 mmol) were successively
added into a Schlenk reaction tube. The mixture was stirred
vigorously at 120 °C for 12 h. After the reaction mixture was
cooled to room temperature, alkyl halides 6 (1.0 mmol) were
added. The resulting mixture was stirred vigorously at room
temperature for another 6 h, then it was cooled to room temp-
erature and concentrated under reduced pressure, and the
residue was purified by flash column chromatography (SiO2)
(eluent: petroleum ether; petroleum ether–ethyl acetate = 10 : 1
for products derived from 4-dimethylaminophenyl chloride) to
obtain the pure product 7.
Experimental
General remarks
Compound 4a:11 white solid (179.7 mg, 99%); 1H NMR
(300 MHz, CDCl3, TMS) δ 7.77 (d, J = 7.5 Hz, 2H), 7.37–7.21 (m,
9H), 7.07–7.05 (m, 2H), 5.04 (s, 1H); 13C NMR (75 MHz, CDCl3)
δ 147.9, 141.6, 141.0, 128.7, 128.3, 127.3, 126.8, 125.3, 119.8,
54.4.
Melting points are uncorrected. NMR spectra were recorded at
1
300/500/600 (for H NMR) or 75/125/150 MHz (for 13C NMR),
1
respectively. H NMR and 13C NMR spectra recorded in CDCl3
solutions were referenced to TMS (0.00 ppm) and the residual
solvent peak (77.0 ppm), respectively. J-values are in Hz.
Organic solvents used were dried by standard methods. The
mass analyzer type for the high-resolution mass spectra was EI
(70 eV) and ESI (quadrupole). Other commercially obtained
reagents were used without further purification. Flash column
chromatography was performed on silica gel.
Compound 4b:12 white solid (191.8 mg, 94%); 1H NMR
(600 MHz, CDCl3, TMS) δ 7.75 (d, J = 7.2 Hz, 2H), 7.34–7.30 (m,
4H), 7.20 (t, J = 7.2 Hz, 2H), 7.15 (t, J = 7.8 Hz, 1H), 6.95 (d, J =
8.4 Hz, 1H), 6.70 (t, J = 7.2 Hz, 1H), 6.58 (s, 1H), 5.65 (s, 1H),
3.89 (s, 3H); 13C NMR (150 MHz, CDCl3) δ 158.0, 148.2, 141.3,
130.4, 128.5, 127.8, 127.1, 127.0, 125.2, 120.9, 119.7, 111.1,
55.7, 47.6.
Compound 4c: white solid (196.0 mg, 96%); mp: 89–90 °C;
1H NMR (300 MHz, CDCl3, TMS) δ 7.74 (d, J = 7.2 Hz, 2H),
7.32–7.28 (m, 4H), 7.22–7.11 (m, 3H), 6.74–6.61 (m, 3H), 4.96
General procedure for the NHC–Pd(II)–Im complex-catalyzed
reactions of fluorenes with aryl chlorides
Under a N2 atmosphere, fluorenes 2 (1.0 mmol), NHC–Pd(II)– (s, 1H), 3.63 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 159.7, 147.6,
Im complex 1 (0.01 mmol), KOtBu (1.125 mmol), dioxane 143.1, 140.9, 129.6, 127.25, 127.22, 125.2, 120.7, 119.8, 114.1,
(2.0 mL) and aryl chlorides 3 (0.75 mmol) were successively 111.8, 55.0, 54.3; MS (EI, %) m/z 272 (M+, 100), 241 (32), 227
added into a Schlenk reaction tube. The mixture was stirred (23), 165 (30), 115 (28); HRMS (EI) calcd for C20H16O:
vigorously at 120 °C for 12 h, then it was cooled to room temp- 272.1201, found: 272.1197.
erature and concentrated under reduced pressure. The residue
Compound 4d:11 white solid (192.0 mg, 94%); 1H NMR
was purified by flash column chromatography (SiO2) (eluent: (300 MHz, CDCl3, TMS) δ 7.73 (d, J = 7.5 Hz, 2H), 7.33–7.16 (m,
petroleum ether; petroleum ether–ethyl acetate = 10 : 1 for pro- 6H), 6.95 (d, J = 8.7 Hz, 2H), 6.75 (d, J = 8.7 Hz, 2H), 4.93 (s,
ducts derived from 4-dimethylaminophenyl chloride) to give 1H), 3.66 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 158.5, 148.1,
the pure products 4.
140.8, 133.4, 129.2, 127.2, 127.1, 125.2, 119.7, 114.0, 55.0, 53.6.
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Compound 4e:7 white solid (mixture of two rotamers, syn/ J = 8.5 Hz, 2H), 6.64 (d, J = 8.5 Hz, 2H), 4.97 (s, 1H), 2.89 (s,
anti
63/37) (190.1 mg, 99%); (syn-rotamer) 1H NMR 6H); 13C NMR (125 MHz, CDCl3) δ 149.5, 148.6, 140.9, 128.9,
(300 MHz, CDCl3, TMS) δ 7.77 (d, J = 7.5 Hz, 2H), 7.33 (t, J = 127.2, 127.0, 125.3, 119.7, 112.9, 53.6, 40.7.
=
6.6 Hz, 3H), 7.27–7.17 (m, 7H), 5.37 (s, 1H), 2.72 (s, 3H);
Compound 4m:16 pale yellow solid (134.9 mg, 74%); 1H NMR
13C NMR (75 MHz, CDCl3) δ 148.4, 141.1, 140.1, 138.4, 136.0, (300 MHz, CDCl3, TMS) δ 8.60 (dq, J = 5.1, 0.9 Hz, 1H), 7.78 (d,
132.6, 130.3, 127.2, 127.1, 125.0, 124.6, 119.9, 49.9, 20.4; (anti- J = 7.5 Hz, 2H), 7.43–7.34 (m, 5H), 7.24 (dt, J = 7.5, 1.2 Hz, 2H),
rotamer) 1H NMR (300 MHz, CDCl3, TMS) δ 7.56 (d, J = 6.9 Hz, 7.08 (ddd, J = 7.5, 5.1, 1.2 Hz, 1H), 6.65 (dt, J = 7.5, 1.2 Hz, 1H),
2H), 7.07 (t, J = 6.9 Hz, 3H), 6.94–6.84 (m, 4H), 6.36 (d, J = 7.5 5.35 (s, 1H); 13C NMR (75 MHz, CDCl3) δ 161.4, 149.2, 146.1,
Hz, 3H), 4.97 (s, 1H), 1.12 (s, 3H); 13C NMR (75 MHz, CDCl3) 141.1, 136.7, 127.5, 127.2, 125.3, 121.8, 121.4, 119.9, 56.4.
δ 146.8, 140.8, 140.1, 137.3, 136.0, 131.6, 127.5, 126.6, 126.5,
125.7, 124.6, 119.9, 56.2, 18.2.
Compound 4n: pale yellow solid (118.5 mg, 65%); mp:
139–140 °C; 1H NMR (300 MHz, CDCl3, TMS) δ 8.59 (s, 1H),
Compound 4f:13 white solid (178.7 mg, 93%); 1H NMR 8.48 (s, 1H), 7.78 (d, J = 7.8 Hz, 2H), 7.40–7.35 (m, 2H),
(300 MHz, CDCl3, TMS) δ 7.77 (d, J = 7.5 Hz, 2H), 7.37–7.11 (m, 7.25–7.21 (m, 4H), 7.13–7.06 (m, 2H), 5.01 (s, 1H); 13C NMR
7H), 7.01 (d, J = 7.5 Hz, 1H), 6.89 (d, J = 7.5 Hz, 1H), 6.85 (s, (75 MHz, CDCl3) δ 149.8, 148.3, 146.7, 140.9, 137.3, 135.2,
1H), 4.98 (s, 1H), 2.23 (s, 3H); 13C NMR (75 MHz, CDCl3) 127.6, 127.4, 125.1, 123.6, 119.9, 51.4; MS (EI, %) m/z 243 (M+,
δ 147.9, 141.4, 140.9, 138.2, 128.8, 128.5, 127.6, 127.24, 127.21, 100), 165 (35); HRMS (EI) calcd for C18H13N: 243.1048, found:
125.5, 125.3, 119.8, 54.4, 21.4.
243.1049.
Compound 4o:17 white solid (190.1 mg, 99%); 1H NMR
Compound 4g:11 white solid (184.4 mg, 96%); 1H NMR
(300 MHz, CDCl3, TMS) δ 7.76 (d, J = 7.5 Hz, 2H), 7.36–7.18 (m, (500 MHz, CDCl3, TMS) δ 7.71 (d, J = 7.5 Hz, 1H), 7.64 (d, J =
6H), 7.04 (d, J = 7.8 Hz, 2H), 6.95 (d, J = 7.8 Hz, 2H), 4.98 (s, 8.0 Hz, 1H), 7.31 (t, J = 7.5 Hz, 1H), 7.24–7.13 (m, 6H),
1H), 2.27 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 148.0, 140.9, 7.09–7.05 (m, 3H), 4.95 (s, 1H), 2.30 (s, 3H); 13C NMR
138.5, 136.3, 129.3, 128.1, 127.24, 127.18, 125.2, 119.8, 54.0, (125 MHz, CDCl3) δ 148.1, 147.7, 141.8, 141.1, 138.3, 137.1,
21.0.
128.6, 128.3, 128.1, 127.2, 126.8, 126.7, 125.9, 125.2, 119.6,
Compound 4h: white solid (156.0 mg, 80%); mp: 119.5, 54.3, 21.6.
1
102–103 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.78 (d, J = 7.5
Compound 4p: yellow solid (212.4 mg, 99%); mp: 84–85 °C;
Hz, 2H), 7.38–7.34 (m, 4H), 7.24 (t, J = 7.5 Hz, 2H), 7.18–7.10 1H NMR (600 MHz, CDCl3, TMS) δ 7.71 (d, J = 7.8 Hz, 1H), 7.64
(m, 2H), 6.88 (t, J = 7.5 Hz, 1H), 6.66 (t, J = 7.5 Hz, 1H), 5.47 (s, (d, J = 7.8 Hz, 1H), 7.31 (t, J = 7.2 Hz, 2H), 7.18–7.14 (m, 3H),
1H); 13C NMR (125 MHz, CDCl3) δ 161.5 (d, JC–F = 243.6 Hz), 6.97 (d, J = 8.4 Hz, 1H), 6.71 (t, J = 7.2 Hz, 2H), 6.59 (s, 1H),
146.8, 141.1, 129.2 (d, JC–F = 4.0 Hz), 128.6 (d, JC–F = 14.9 Hz), 5.61 (s, 1H), 3.92 (s, 3H), 2.33 (s, 3H); 13C NMR (150 MHz,
128.3 (d, JC–F = 8.0 Hz), 127.4 (d, JC–F = 7.5 Hz), 125.2, 124.3 (d, CDCl3) δ 158.0, 148.5, 148.2, 141.4, 138.7, 136.9, 130.7, 128.6,
JC–F = 3.5 Hz), 119.9, 115.5 (d, JC–F = 22.1 Hz), 46.9; MS (EI, %) 127.9, 127.7, 126.9, 126.6, 125.9, 125.2, 121.0, 119.5, 119.4,
m/z 260 (M+, 100), 165 (25), 120 (19); HRMS (EI) calcd for 111.1, 55.8, 47.4, 21.6; MS (EI, %) m/z 286 (M+, 100), 271 (70),
C19H13F: 260.1001, found: 260.0999.
Compound 4i:14 white solid (152.1 mg, 78%); 1H NMR 286.1358, found: 286.1356.
(300 MHz, CDCl3, TMS) δ 7.75 (d, J = 7.5 Hz, 2H), 7.34 (t, J = Compound 4q: pale yellow solid (190.9 mg, 89%); mp:
255 (44), 239 (35), 178 (26); HRMS (EI) calcd for C21H18O:
1
7.2 Hz, 2H), 7.28–7.12 (m, 5H), 6.90–6.84 (m, 2H), 6.72 (dt, J = 102–103 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.72 (d, J = 7.5
9.6, 1.8 Hz, 1H), 4.97 (s, 1H); 13C NMR (75 MHz, CDCl3) Hz, 1H), 7.65 (d, J = 7.5 Hz, 1H), 7.32 (t, J = 7.5 Hz, 1H), 7.25
δ 163.0 (d, JC–F = 244.6 Hz), 147.1, 144.2 (d, JC–F = 6.9 Hz), 141.0, (d, J = 7.5 Hz, 1H), 7.19 (t, J = 7.5 Hz, 1H), 7.15 (d, J = 7.5 Hz,
130.0 (d, JC–F = 8.1 Hz), 127.4 (d, JC–F = 17.9 Hz), 125.2, 124.0, 1H), 7.09 (s, 1H), 6.98 (d, J = 8.5 Hz, 2H), 6.78 (d, J = 8.5 Hz,
119.9, 115.0 (d, JC–F = 21.4 Hz), 113.7 (d, JC–F = 22.3 Hz), 54.0.
2H), 4.92 (s, 1H), 3.72 (s, 3H), 2.32 (s, 3H); 13C NMR (125 MHz,
Compound 4j:11 white solid (181.3 mg, 93%); 1H NMR CDCl3) δ 158.4, 148.4, 148.0, 140.9, 138.2, 137.1, 133.7, 129.3,
(300 MHz, CDCl3, TMS) δ 7.75 (d, J = 7.8 Hz, 2H), 7.36–7.31 (m, 128.0, 127.1, 126.7, 125.8, 125.2, 119.5, 119.4, 114.0, 55.1, 53.5,
2H), 7.25–7.18 (m, 4H), 7.01–6.97 (m, 2H), 6.93–6.87 (m, 2H), 21.6; MS (EI, %) m/z 286 (M+, 100), 271 (84), 255 (29), 239 (22),
4.95 (s, 1H); 13C NMR (125 MHz, CDCl3) δ 161.8 (d, JC–F = 243.5 226 (23); HRMS calcd for C21H18O: 286.1358, found: 286.1355.
Hz), 147.7, 140.9, 137.3 (d, JC–F = 3.1 Hz), 129.7 (d, JC–F = 7.9
Hz), 127.4 (d, JC–F = 8.9 Hz), 125.2, 119.9, 115.5 (d, JC–F = 21.1 1H NMR (500 MHz, CDCl3, TMS) δ 7.72 (d, J = 7.5 Hz, 1H), 7.64
Hz), 53.6. (d, J = 7.5 Hz, 1H), 7.32 (t, J = 7.5 Hz, 1H), 7.26 (d, J = 7.5 Hz,
Compound 4r: white solid (180.2 mg, 89%); mp: 68–69 °C;
Compound 4k:7 white solid (185.0 mg, 91%); 1H NMR 1H), 7.20–7.10 (m, 4H), 7.01 (d, J = 7.5 Hz, 1H), 6.89 (d, J =
(500 MHz, CDCl3, TMS) δ 7.81 (d, J = 7.5 Hz, 2H), 7.37 (t, J = 7.5 Hz, 1H), 6.85 (s, 1H), 4.93 (s, 1H), 2.31 (s, 3H), 2.23 (s, 3H);
7.5 Hz, 2H), 7.25–7.17 (m, 5H), 7.07 (t, J = 7.5 Hz, 1H), 6.80 (d, 13C NMR (125 MHz, CDCl3) δ 148.2, 147.8, 141.6, 141.0, 138.3,
J = 7.5 Hz, 1H), 5.51 (s, 1H), 2.69 (s, 3H), 1.11 (s, 3H); 13C NMR 138.2, 137.1, 128.9, 128.5, 128.1, 127.6, 127.1, 126.7, 125.9,
(125 MHz, CDCl3) δ 146.9, 140.9, 138.0, 137.7, 136.9, 129.7, 125.5, 125.2, 119.5, 119.4, 54.2, 21.6, 21.4; MS (EI, %) m/z 270
128.0, 127.2, 126.83, 126.79, 124.1, 120.0, 50.0, 21.8, 18.7.
Compound 4l:15 yellow solid (175.3 mg, 82%); 1H NMR C21H18: 270.1409, found: 270.1410.
(500 MHz, CDCl3, TMS) δ 7.77 (d, J = 7.5 Hz, 2H), 7.35 (d, J = Compound 4s: white solid (179.0 mg, 88%); mp:
7.5 Hz, 2H), 7.32 (d, J = 7.5 Hz, 2H), 7.25–7.22 (m, 2H), 6.96 (d, 102–105 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.71 (d, J = 7.5
(M+, 96), 255 (100), 239 (27), 178 (23); HRMS (EI) calcd for
1
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Hz, 1H), 7.64 (d, J = 8.0 Hz, 1H), 7.31 (t, J = 7.5 Hz, 1H),
Compound 4y: white solid (156.2 mg, 76%); mp: 98–99 °C;
7.25 (d, J = 7.5 Hz, 1H), 7.17 (t, J = 7.5 Hz, 1H), 7.14 (d, J = 1H NMR (500 MHz, CDCl3, TMS) δ 7.90 (d, J = 8.0 Hz, 1H), 7.36
8.0 Hz, 1H), 7.09 (s, 1H), 7.05 (d, J = 8.0 Hz, 2H), 6.95 (d, J = (t, J = 7.5 Hz, 1H), 7.26 (d, J = 7.5 Hz, 1H), 7.21 (dt, J = 7.5, 1.0
8.0 Hz, 2H), 4.93 (s, 1H), 2.30 (s, 3H), 2.27 (s, 3H); 13C NMR Hz, 1H), 7.13–7.12 (m, 2H), 7.09 (dd, J = 8.5, 4.0 Hz, 1H), 6.98
(125 MHz, CDCl3) δ 148.3, 147.9, 141.0, 138.7, 138.3, 137.1, (dd, J = 8.5, 5.5 Hz, 2H), 6.90 (t, J = 8.5 Hz, 2H), 4.92 (s, 1H),
136.2, 129.3, 128.2, 128.1, 127.1, 126.7, 125.9, 125.2, 119.5, 2.72 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 161.8 (d, JC–F = 243.3
119.4, 53.9, 21.6, 21.0; MS (EI, %) m/z 270 (M+, 94), 255 (100), Hz), 148.1 (d, JC–F = 3.5 Hz), 141.9, 138.9, 137.6 (d, JC–F = 3.1
239 (27), 178 (18); HRMS (EI) calcd for C21H18: 270.1409, Hz), 133.0, 129.8 (d, JC–F = 7.8 Hz), 129.6, 127.3, 127.0, 126.6,
found: 270.1414.
125.1, 123.1, 122.7, 115.4 (d, JC–F = 21.4 Hz), 53.5, 21.0; MS (EI,
Compound 4t: white solid (164.4 mg, 80%); mp: 80–81 °C; %) m/z 274 (M+, 80), 259 (100); HRMS (EI) calcd for C20H15F:
1H NMR (500 MHz, CDCl3, TMS) δ 7.71 (d, J = 7.5 Hz, 1H), 7.64 274.1158, found: 274.1161.
(d, J = 7.5 Hz, 1H), 7.32 (t, J = 7.5 Hz, 1H), 7.22–7.12 (m, 3H),
7.06 (s, 1H), 7.01–6.98 (m, 2H), 6.91 (t, J = 8.5 Hz, 2H), 4.92 (s, 141–142 °C; 1H NMR (500 MHz, CDCl3, TMS) δ 7.92 (d, J =
1H), 2.31 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 161.8 (d, JC–F
8.0 Hz, 1H), 7.38–7.33 (m, 2H), 7.25–7.22 (m, 1H), 7.18–7.11
Compound 4z: yellow solid (192.9 mg, 86%); mp:
=
243.3 Hz), 148.0, 147.6, 141.0, 138.2, 137.5 (d, JC–F = 3.1 Hz), (m, 3H), 6.95 (d, J = 8.5 Hz, 2H), 6.65 (d, J = 8.5 Hz, 2H), 4.94
137.3, 129.8, 129.7, 128.3, 127.3, 126.8, 125.8, 125.1, 119.6 (d, (s, 1H), 2.90 (s, 6H), 2.76 (s, 3H); 13C NMR (125 MHz, CDCl3)
JC–F = 9.3 Hz), 115.5 (d, JC–F = 21.4 Hz), 53.4, 21.6; MS (EI, %) δ 149.03, 148.99, 141.9, 138.9, 132.8, 129.3, 129.0, 126.93,
m/z 274 (M+, 86), 259 (100); HRMS (EI) calcd for C20H15F: 126.85, 126.5, 125.2, 122.9, 122.8, 113.0, 53.6, 40.7, 21.0; MS
274.1158, found: 274.1156.
Compound 4u: yellow solid (195.1 mg, 87%); mp: 300.1746, found: 300.1752.
(ESI): 300 [M + H]+; HRMS (ESI) calcd for C22H22N: [M + H]+:
1
149–150 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.72 (d, J = 7.5
Compound 4aa: yellow solid (200.1 mg, 92%); mp:
Hz, 1H), 7.65 (d, J = 8.0 Hz, 1H), 7.33–7.28 (m, 2H), 7.21–7.13 67–68 °C; 1H NMR (500 MHz, CDCl3, TMS) δ 7.69–7.65 (m,
(m, 3H), 6.95 (d, J = 8.5 Hz, 2H), 6.64 (d, J = 8.5 Hz, 2H), 4.91 2H), 7.33 (t, J = 7.5 Hz, 1H), 7.28 (d, J = 7.5 Hz, 1H), 7.20 (dt,
(s, 1H), 2.88 (s, 6H), 2.33 (s, 3H); 13C NMR (125 MHz, CDCl3) J = 7.5, 1.0 Hz, 1H), 7.16 (t, J = 7.5 Hz, 1H), 7.05–6.99 (m, 2H),
δ 149.5, 148.8, 148.5, 141.0, 138.2, 137.0, 129.4, 129.0, 127.9, 6.75 (dd, J = 8.5, 2.5 Hz, 1H), 6.65 (d, J = 7.5 Hz, 1H), 6.59 (t, J =
126.9, 126.7, 125.9, 125.2, 119.44, 119.36, 112.8, 53.5, 40.6, 2.0 Hz, 1H), 4.93 (s, 1H), 3.67 (s, 3H); 13C NMR (125 MHz,
21.6; MS (ESI): 300 [M + H]+; HRMS (EI) calcd for C22H22N CDCl3) δ 162.6 (d, JC–F = 244.0 Hz), 159.8, 149.7 (d, JC–F
[M + H]+: 300.1747, found: 300.1752.
8.1 Hz), 147.4 (d, JC–F = 1.9 Hz), 142.4, 140.1, 136.9 (d, JC–F
=
=
Compound 4v: white solid (163.0 mg, 85%); mp: 2.3 Hz), 129.7, 127.4, 126.9, 125.2, 120.8 (d, JC–F = 8.8 Hz),
1
106–107 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.89 (d, J = 7.5 120.6, 119.5, 114.5 (d, JC–F = 22.9 Hz), 114.1, 112.5 (d, JC–F
=
Hz, 1H), 7.34 (t, J = 7.5 Hz, 1H), 7.28 (d, J = 7.0 Hz, 1H), 22.9 Hz), 112.0, 55.0, 54.3 (d, JC–F = 2.1 Hz); MS (EI, %) m/z 290
7.22–7.15 (m, 4H), 7.12–7.11 (m, 3H), 7.03 (d, J = 7.5 Hz, 2H), (M+, 100), 259 (37), 183 (28); HRMS (EI) calcd for C20H15FO:
4.95 (s, 1H), 2.71 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 148.31, 290.1107, found: 290.1111.
148.27, 141.93, 141.91, 139.0, 132.9, 129.5, 128.6, 128.3, 127.1,
Compound 4ab: yellow solid (179.0 mg, 82%); mp:
126.9, 126.7, 126.6, 125.2, 123.0, 122.8, 54.3, 21.0; MS (EI, %) 99–100 °C; 1H NMR (500 MHz, CDCl3, TMS) δ 7.70–7.66 (m,
m/z 256 (M+, 85), 241 (100); HRMS calcd for C20H16: 256.1252, 2H), 7.34 (t, J = 7.5 Hz, 1H), 7.26 (d, J = 7.5 Hz, 1H), 7.21 (dt,
found: 256.1254.
J = 7.5, 1.0 Hz, 1H), 7.04 (dt, J = 9.0, 2.0 Hz, 1H), 6.98–6.95 (m,
Compound 4w: pale yellow solid (198.0 mg, 92%); mp: 3H), 6.79 (d, J = 8.5 Hz, 2H), 4.92 (s, 1H), 3.72 (s, 3H); 13C NMR
1
102–103 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.88 (d, J = 8.0 (125 MHz, CDCl3) δ 162.6 (d, JC–F = 243.9 Hz), 158.6, 150.3 (d,
Hz, 1H), 7.33 (t, J = 7.5 Hz, 1H), 7.27 (d, J = 7.5 Hz, 1H), 7.19 JC–F = 8.0 Hz), 148.0 (d, JC–F = 1.8 Hz), 140.0, 136.8 (d, JC–F
=
(dt, J = 7.5, 0.5 Hz, 1H), 7.09–7.11 (m, 3H), 6.94 (d, J = 8.5 Hz, 2.1 Hz), 132.7, 129.2, 127.3, 126.9, 125.2, 120.7 (d, JC–F = 8.8
2H), 6.74 (d, J = 8.5 Hz, 2H), 4.90 (s, 1H), 3.66 (s, 3H), 2.70 (s, Hz), 119.5, 114.4 (d, JC–F = 22.9 Hz), 114.1, 112.5 (d, JC–F = 22.8
3H); 13C NMR (125 MHz, CDCl3) δ 158.4, 148.58, 148.55, 141.8, Hz), 55.1, 53.6; MS (EI, %) m/z 290 (M+, 100), 259 (42); HRMS
133.8, 129.4, 129.3, 127.0, 126.9, 126.5, 125.1, 122.9, 122.7, (EI) calcd for C20H15FO: 290.1107, found: 290.1108.
114.0, 55.0, 53.5, 21.0; MS (EI, %) m/z 286 (M+, 100), 271 (99);
HRMS (EI) calcd for C21H18O: 286.1358, found: 286.1357.
Compound 4ac: colorless liquid (170.6 mg, 83%); (mixture
of two rotamers, syn/anti = 64/36) (syn-rotamer) 1H NMR
Compound 4x: white solid (176.2 mg, 87%); mp: (500 MHz, CDCl3, TMS) δ 7.72–7.66 (m, 3H), 7.35–7.32 (m,
1
100–101 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.89 (d, J = 7.5 1H), 7.28–7.25 (m, 1H), 7.20–7.15 (m, 2H), 7.10–7.07 (m, 1H),
Hz, 1H), 7.34 (t, J = 8.0 Hz, 1H), 7.28 (d, J = 7.0 Hz, 1H), 7.20 6.96–6.93 (m, 2H), 6.35 (d, J = 7.5 Hz, 1H), 5.32 (s, 1H), 2.71 (s,
(dt, J = 7.5, 1.0 Hz, 1H), 7.14–7.10 (m, 3H), 7.03 (d, J = 8.0 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 162.6 (d, JC–F = 243.9 Hz),
2H), 6.93 (d, J = 8.0 Hz, 2H), 4.93 (s, 1H), 2.71 (s, 3H), 2.26 (s, 150.5 (d, JC–F = 8.1 Hz), 148.2, 140.2, 139.4, 136.0, 132.5, 131.7,
3H); 13C NMR (125 MHz, CDCl3) δ 148.51, 148.47, 141.9, 138.9, 130.4, 127.4, 127.3, 126.9, 126.8, 126.5, 125.0, 120.8, 119.6,
138.8, 136.2, 132.9, 129.4, 129.3, 128.2, 127.1, 126.9, 126.5, 114.3 (d, JC–F = 22.9 Hz), 112.3 (d, JC–F = 22.8 Hz), 49.9, 20.4;
125.2, 123.0, 122.8, 54.0, 21.03, 21.02; MS (EI, %) m/z 270 (M+, (anti-rotamer) 1H NMR (500 MHz, CDCl3, TMS) δ 7.72–7.66 (m,
90), 255 (100), 239 (24), 178 (31); HRMS (EI) calcd for C21H18: 3H), 7.53 (d, J = 7.5 Hz, 1H), 7.35–7.32 (m, 1H), 7.28–7.25 (m,
270.1409, found: 270.1406.
1H), 7.20–7.15 (m, 2H), 7.05–7.03 (m, 1H), 6.91–6.88 (m, 2H),
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4.92 (s, 1H), 1.15 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 162.7 6H), 7.17 (t, J = 7.5 Hz, 2H), 6.71 (d, J = 9.0 Hz, 2H), 3.65 (s,
(d, JC–F = 244.1 Hz), 149.0 (d, JC–F = 8.0 Hz), 146.7, 139.9, 137.7, 3H), 2.68 (s, 1H); 13C NMR (125 MHz, CDCl3) δ 158.6, 150.5,
137.2, 137.1, 136.8, 130.4, 127.5, 127.2, 126.9, 126.8, 125.8, 139.4, 135.3, 128.9, 128.3, 126.5, 124.6, 119.9, 113.5, 83.2, 55.0.
125.0, 124.6, 120.8, 119.6, 114.3 (d, JC–F = 22.9 Hz), 112.0 (d,
Compound 5e:20 white solid (132.6 mg, 65%); 1H NMR
JC–F = 22.8 Hz), 56.1, 18.2; MS (EI, %) m/z 274 (M+, 100), 259 (500 MHz, CDCl3, TMS) δ 7.59 (d, J = 7.5 Hz, 2H), 7.29 (td, J =
(42), 183 (43); HRMS (EI) calcd for C20H15F: 274.1158, found: 7.5, 1.5 Hz, 2H), 7.25 (d, J = 8.0 Hz, 2H), 7.21 (d, J = 7.5 Hz,
274.1154.
2H), 7.17 (td, J = 7.5, 1.0 Hz, 2H), 7.02 (d, J = 8.0 Hz, 2H), 2.49
Compound 4ad: white solid (170.6 mg, 83%); mp: (s, 1H), 2.25 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 150.5, 140.2,
1
132–133 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.69 (d, J = 7.5 139.5, 136.7, 128.9, 128.8, 128.3, 125.2, 124.7, 120.0, 83.4, 21.0.
Hz, 1H), 7.66 (dd, J = 8.0, 5.0 Hz, 1H), 7.33 (t, J = 7.5 Hz, 1H),
Compound 5f: white solid (140.7 mg, 68%); mp: 94–95 °C;
7.26 (d, J = 7.5 Hz, 1H), 7.20 (t, J = 7.5 Hz, 1H), 7.06 (d, J = 1H NMR (500 MHz, CDCl3, TMS) δ 7.91 (td, J = 8.0, 1.5 Hz, 1H),
7.5 Hz, 2H), 7.02 (d, J = 8.0 Hz, 1H), 6.98 (d, J = 7.5 Hz, 1H), 7.65 (d, J = 7.5 Hz, 2H), 7.35 (t, J = 7.0 Hz, 2H), 7.28 (d, J =
6.94 (d, J = 7.5 Hz, 2H), 4.93 (s, 1H), 2.28 (s, 3H); 13C NMR 7.5 Hz, 2H), 7.23–7.15 (m, 4H), 6.83 (dd, J = 11.0, 8.0 Hz, 1H),
(125 MHz, CDCl3) δ 162.6 (d, JC–F = 244.0 Hz), 150.2 (d, JC–F
=
2.62 (s, 1H); 13C NMR (125 MHz, CDCl3) δ 159.7 (d, JC–F = 247.3
8.0 Hz), 147.9, 140.1, 137.8, 136.9 (d, JC–F 2.0 Hz), Hz), 149.1, 139.8, 130.2 (d, JC–F = 10.8 Hz), 129.2, 129.1 (d,
=
136.6, 129.5, 128.1, 127.4, 126.9, 125.2, 120.7 (d, JC–F = 8.8 Hz), JC–F = 8.4 Hz), 128.3, 127.9 (d, JC–F = 3.3 Hz), 124.0, 123.8 (d,
119.5, 114.4 (d, JC–F = 22.9 Hz), 112.5 (d, JC–F = 22.9 Hz), 54.1 JC–F = 3.5 Hz), 120.1, 115.8 (d, JC–F = 21.8 Hz), 81.2; MS (ESI):
(d, JC–F = 1.9 Hz), 21.0; MS (EI, %) m/z 274 (M+, 100), 259 (58), 299 [M + Na]+; HRMS (ESI) calcd for C19H13FNaO [M + H]+:
183 (22); HRMS (EI) calcd for C20H15F: 274.1158, found: 299.0830, found: 299.0848.
1
274.1154.
Compound 5g: pale yellow liquid (124.2 mg, 60%); H NMR
Compound 4ae: red solid (211.4 mg, 93%); mp: 131–132 °C; (500 MHz, CDCl3, TMS) δ 7.61 (d, J = 7.5 Hz, 2H), 7.31 (td, J =
1H NMR (500 MHz, CDCl3, TMS) δ 7.72–7.68 (m, 2H), 7.35 (t, 7.5, 1.0 Hz, 2H), 7.23 (d, J = 7.0 Hz, 2H), 7.19 (td, J = 7.5,
J = 7.5 Hz, 1H), 7.30 (d, J = 7.5 Hz, 1H), 7.22 (t, J = 7.5 Hz, 1H), 1.0 Hz, 2H), 7.15–7.11 (m, 2H), 7.01 (dt, J = 9.0, 1.0 Hz, 1H),
7.07–7.00 (m, 2H), 6.95 (d, J = 8.5 Hz, 2H), 6.67 (d, J = 8.5 Hz, 6.88–6.84 (m, 1H), 2.59 (s, 1H); 13C NMR (125 MHz, CDCl3)
2H), 4.94 (s, 1H), 2.91 (s, 6H); 13C NMR (125 MHz, CDCl3) δ 162.8 (d, JC–F = 243.8 Hz), 149.9, 146.0 (d, JC–F = 7.0 Hz),
δ 162.7 (d, JC–F = 243.6 Hz), 150.8 (d, JC–F = 8.0 Hz), 149.6, 139.5, 129.6 (d, JC–F = 8.1 Hz), 129.2, 128.5, 124.6, 121.1 (d, JC–F
148.4, 140.1, 136.8 (d, JC–F = 2.1 Hz), 135.0, 128.9, 128.8, 127.2, = 2.8 Hz), 120.1, 114.0 (d, JC–F = 21.0 Hz), 112.7 (d, JC–F = 22.8
126.9, 125.3, 120.6 (d, JC–F = 8.8 Hz), 119.4, 114.3 (d, JC–F = 22.9 Hz), 83.1 (d, JC–F = 1.9 Hz); MS (ESI): 259 [M + H − H2O]+;
Hz), 113.7, 113.0, 112.6 (d, JC–F = 22.8 Hz), 53.7 (d, JC–F = 2.1 HRMS (ESI) calcd for C19H12F [M + H − H2O]+: 259.0923,
Hz), 40.7; MS (ESI): 304 [M + H]+; HRMS (ESI) calcd for found: 259.0919.
C21H19FN 304 [M + H]+: 304.1500, found: 304.1502.
Compound 5h:20 white solid (140.7 mg, 68%); 1H NMR
Compound 5a:18 yellow solid (123.9 mg, 64%); 1H NMR (500 MHz, CDCl3, TMS) δ 7.59 (d, J = 7.5 Hz, 2H), 7.29 (td, J =
(500 MHz, CDCl3, TMS) δ 7.61 (d, J = 7.5 Hz, 2H), 7.34–7.29 (m, 7.0, 1.5 Hz, 2H), 7.27–7.23 (m, 2H), 7.20–7.15 (m, 4H),
4H), 7.25 (d, J = 7.0 Hz, 2H), 7.22–7.15 (m, 5H), 2.52 (s, 1H); 6.88–6.84 (m, 2H), 2.65 (s, 1H); 13C NMR (125 MHz, CDCl3)
13C NMR (125 MHz, CDCl3) δ 150.4, 143.1, 139.5, 129.0, 128.4, δ 162.0 (d, JC–F = 243.8 Hz), 150.1, 139.4, 138.9 (d, JC–F
=
128.1, 127.1, 125.3, 124.7, 120.0, 83.5.
Compound 5b: white solid (181.4 mg, 84%); mp: 74–75 °C; 114.9 (d, JC–F = 21.3 Hz), 83.1.
1H NMR (500 MHz, CDCl3, TMS) δ 7.60 (d, J = 7.5 Hz, 2H), 7.44 Compound 5i:21 white solid (103.0 mg, 53%); 1H NMR
3.0 Hz), 129.1, 128.4, 127.1 (d, JC–F = 8.1 Hz), 124.6, 120.1,
(d, J = 7.5 Hz, 2H), 7.29 (td, J = 7.5, 1.0 Hz, 2H), 7.21–7.15 (m, (500 MHz, CDCl3, TMS) δ 8.16 (d, J = 1.5 Hz, 1H), 8.02 (d, J =
3H), 7.11–7.03 (m, 1H), 6.84 (d, J = 8.0 Hz, 1H), 6.77 (t, J = 5.5 Hz, 1H), 7.66 (d, J = 8.0 Hz, 1H), 7.53 (d, J = 7.5 Hz, 2H),
7.5 Hz, 1H), 4.87 (br, 1H), 3.66 (s, 3H); 13C NMR (125 MHz, 7.29–7.25 (m, 2H), 7.18–7.13 (m, 4H), 7.03 (dd, J = 8.0, 5.0 Hz,
CDCl3) δ 157.3, 149.9, 139.7, 131.5, 128.64, 128.63, 127.9, 1H), 5.16 (s, 1H); 13C NMR (125 MHz, CDCl3) δ 149.9, 147.4,
127.2, 124.2, 120.8, 119.7, 111.9, 84.0, 55.5; MS (ESI): 327 146.6, 139.6, 139.4, 133.4, 129.1, 128.3, 124.7, 122.9, 120.0,
[M + K]+; HRMS (ESI) calcd for C20H16KO2 [M + H]+: 327.0787, 81.9.
found: 327.0779.
Compound 5j: purple liquid (169.9 mg, 75%); 1H NMR
Compound 5c: white solid (155.6 mg, 72%); mp: 71–72 °C; (500 MHz, CDCl3, TMS) δ 7.54 (d, J = 7.5 Hz, 1H), 7.46 (d, J =
1H NMR (500 MHz, CDCl3, TMS) δ 7.57 (d, J = 7.5 Hz, 2H), 7.5 Hz, 1H), 7.28–7.21 (m, 4H), 7.14 (t, J = 7.5 Hz, 1H), 7.09 (d,
7.29–7.25 (m, 4H), 7.16 (td, J = 7.5, 1.0 Hz, 2H), 7.07 (t, J = 8.0 J = 9.0 Hz, 2H), 6.72 (d, J = 9.0 Hz, 2H), 3.65 (s, 3H), 2.60 (s,
Hz, 1H), 7.00 (t, J = 2.0 Hz, 1H), 6.81 (d, J = 8.0 Hz, 1H), 6.68 1H), 2.27 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 158.6, 150.7,
(dd, J = 8.5, 3.5 Hz, 1H), 3.64 (s, 3H), 2.68 (s, 1H); 13C NMR 150.5, 139.5, 138.3, 136.7, 135.5, 129.6, 128.8, 127.8, 126.5,
(125 MHz, CDCl3) δ 159.4, 150.2, 144.9, 139.5, 129.1, 128.9, 125.3, 124.5, 119.7, 119.6, 113.5, 83.1, 55.0, 21.5; MS (ESI): 341
128.3, 124.6, 119.9, 117.9, 112.3, 111.3, 83.4, 55.0; MS (ESI): [M + K]+; HRMS (ESI) calcd for C21H18KO2 [M + H]+: 341.0944,
271 [M + H − H2O]+; HRMS (ESI) calcd for C20H15O [M + H − found: 341.0933.
H2O]+: 271.1123, found: 271.1108.
Compound 5k: brown liquid (160.9 mg, 75%); 1H NMR
Compound 5d:19 white solid (149.0 mg, 69%); 1H NMR (500 MHz, CDCl3, TMS) δ 7.54 (d, J = 7.5 Hz, 1H), 7.47 (d, J =
(500 MHz, CDCl3, TMS) δ 7.58 (d, J = 7.5 Hz, 2H), 7.30–7.23 (m, 7.5 Hz, 1H), 7.26 (t, J = 7.5 Hz, 1H), 7.23–7.20 (m, 3H), 7.13
8494 | Org. Biomol. Chem., 2014, 12, 8488–8498
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(t, J = 7.5 Hz, 1H), 7.09–7.07 (m, 2H), 7.01 (d, J = 8.0 Hz, 2H), J = 7.5 Hz, 2H), 3.75 (s, 2H), 2.20 (s, 3H); 13C NMR (125 MHz,
2.47 (s, 1H), 2.26 (s, 3H), 2.24 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 150.6, 144.5, 140.8, 137.8, 136.5, 129.9, 128.2, 127.5,
CDCl3) δ 150.9, 150.7, 140.6, 139.8, 138.5, 137.0, 136.8, 129.8, 127.4, 127.1, 127.0, 126.7, 125.6, 125.0, 123.9, 119.7, 59.9, 44.1,
129.0, 128.0, 125.50, 125.49, 124.8, 119.9, 119.8, 83.5, 21.7, 21.6; MS (EI, %) m/z 346 (M+, 4), 255 (100), 239 (24); HRMS (EI)
21.2; MS (ESI): 325 [M + K]+; HRMS (ESI) calcd for C21H18KO calcd for C27H22: 346.1722, found: 346.1720.
[M + K]+: 325.0995, found: 325.0994.
Compound 7e: white solid (257.0 mg, 99%); mp:
Compound 5l: colorless liquid (158.4 mg, 69%); 1H NMR 132–133 °C; 1H NMR (300 MHz, CDCl3, TMS) δ 7.42–7.39 (m,
(500 MHz, CDCl3, TMS) δ 7.54–7.51 (m, 2H), 7.29 (t, J = 7.5 Hz, 2H), 7.31–7.29 (m, 2H), 7.19–7.16 (m, 7H), 7.02 (d, J = 7.8 Hz,
1H), 7.25–7.21 (m, 3H), 7.17 (t, J = 7.5 Hz, 1H), 7.00–6.95 (m, 2H), 6.88–6.63 (m, 2H), 6.42 (d, J = 7.5 Hz, 2H), 3.75 (s, 2H), 2.25
2H), 6.73 (d, J = 9.0 Hz, 2H), 3.67 (s, 3H), 2.76 (s, 1H); 13C NMR (s, 3H); 13C NMR (125 MHz, CDCl3) δ 150.7, 141.6, 140.8, 136.6,
(125 MHz, CDCl3) δ 163.1 (d, JC–F = 245.9 Hz), 158.8, 152.9 (d, 136.1, 130.0, 129.1, 127.1, 127.0, 126.8, 126.7, 125.6, 125.0,
JC–F = 7.3 Hz), 150.4 (d, JC–F = 1.9 Hz), 138.6, 135.2 (d, JC–F = 2.6 119.7, 59.7, 44.1, 20.9; MS (EI, %) m/z 346 (M+, 2), 255 (100), 239
Hz), 134.7, 129.1, 128.0, 126.5, 124.7, 121.1 (d, JC–F = 8.5 Hz), (19); HRMS calcd for C27H22: 346.1722, found: 346.1724.
119.7, 115.8 (d, JC–F = 23.0 Hz), 113.6, 112.2 (d, JC–F = 23.1 Hz),
Compound 7f: white solid (257.3 mg, 98%); mp:
1
83.0 (d, JC–F = 1.9 Hz), 55.1; MS (ESI): 289 [M + H − H2O]+; 153–156 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.45–7.44 (m,
HRMS (ESI) calcd for C20H14FO [M + H − H2O]+: 289.1029, 2H), 7.31–7.30 (m, 2H), 7.23–7.15 (m, 5H), 7.07–7.00 (m, 2H),
found: 289.1022.
6.89–6.84 (m, 2H), 6.76 (t, J = 7.5 Hz, 2H), 6.41 (d, J = 7.5 Hz,
Compound 5m: pale yellow liquid (152.3 mg, 70%); 2H), 3.74 (s, 2H); 13C NMR (125 MHz, CDCl3) δ 162.8 (d, JC–F
=
1H NMR (500 MHz, CDCl3, TMS) δ 7.54–7.51 (m, 2H), 7.29 (td, 243.9 Hz), 149.9, 147.4 (d, JC–F = 6.8 Hz), 140.8, 136.0, 130.0,
J = 7.5, 1.0 Hz, 1H), 7.22 (d, J = 7.5 Hz, 1H), 7.19–7.14 (m, 3H), 129.7 (d, JC–F = 8.3 Hz), 127.4, 127.2, 126.8, 125.8, 124.9, 122.6,
7.02 (d, J = 8.0 Hz, 2H), 6.98 (dt, J = 8.0, 2.5 Hz, 1H), 6.94 (dd, 119.8, 114.1 (d, JC–F = 22.3 Hz), 113.4 (d, JC–F = 20.9 Hz), 59.7,
J = 8.0, 2.5 Hz, 1H), 2.61 (s, 1H), 2.25 (s, 3H); 13C NMR 43.9; MS (EI, %) m/z 350 (M+, 5), 259 (100); HRMS calcd for
(125 MHz, CDCl3) δ 163.1 (d, JC–F = 245.9 Hz), 152.8 (d, JC–F
7.4 Hz), 150.4 (d, JC–F = 2.0 Hz), 139.6, 138.7, 137.0, 135.2 (d,
JC–F = 2.5 Hz), 129.1, 129.0, 128.0, 125.2, 124.7, 121.1 (d, JC–F
=
C26H19F: 350.1471, found: 350.1472.
Compound 7g: white solid (257.5 mg, 98%); mp:
1
=
137–138 °C; H NMR (300 MHz, CDCl3, TMS) δ 7.43–7.38 (m,
8.5 Hz), 119.7, 115.9 (d, JC–F = 23.0 Hz), 112.3 (d, JC–F = 23.1 2H), 7.28–7.17 (m, 8H), 6.90–6.80 (m, 3H), 6.73 (t, J = 7.5 Hz,
Hz), 83.2 (d, JC–F = 1.9 Hz), 21.0; MS (ESI): 273 [M + H − H2O]+; 2H), 6.39 (d, J = 6.9 Hz, 2H), 3.71 (s, 2H); 13C NMR (125 MHz,
HRMS (ESI) calcd for C20H14F [M + H − H2O]+: 273.1080, CDCl3) δ 161.5 (d, JC–F = 243.9 Hz), 150.4, 140.7, 140.3 (d, JC–F
=
found: 273.1061.
3.1 Hz), 136.2, 129.9, 128.4 (d, JC–F = 7.8 Hz), 127.3, 127.1,
Compound 7a:22 white solid (246.5 mg, 99%); 1H NMR 126.8, 125.8, 124.8, 119.8, 115.1 (d, JC–F = 20.9 Hz), 59.4, 44.1;
(500 MHz, CDCl3, TMS) δ 7.43–7.41 (m, 2H), 7.31–7.28 (m, MS (EI, %) m/z 350 (M+, 2), 259 (100); HRMS calcd for C26H19F:
4H), 7.22–7.14 (m, 7H), 6.83 (t, J = 7.5 Hz, 1H), 6.74 (t, J = 350.1471, found: 350.1474.
7.5 Hz, 2H), 6.42 (d, J = 7.5 Hz, 2H), 3.77 (s, 2H); 13C NMR
Compound 7h: pale yellow solid (233.4 mg, 83%); mp:
1
(125 MHz, CDCl3) δ 150.5, 144.5, 140.8, 136.4, 129.9, 128.4, 178–179 °C; H NMR (300 MHz, CDCl3, TMS) δ 7.45–7.44 (m,
127.1, 127.0, 126.8, 126.7, 126.5, 125.6, 125.0, 119.7, 59.9, 43.9. 2H), 7.35–7.33 (m, 2H), 7.23–7.17 (m, 6H), 6.85 (t, J = 7.5 Hz,
Compound 7b: white solid (268.8 mg, 99%); mp: 1H), 6.76 (t, J = 7.5 Hz, 2H), 6.63 (d, J = 7.5 Hz, 2H), 6.43 (d, J =
1
118–119 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.49–7.45 (m, 7.5 Hz, 2H), 3.74 (s, 2H), 2.87 (s, 6H); 13C NMR (125 MHz,
2H), 7.37–7.33 (m, 2H), 7.26–7.22 (m, 4H), 7.18 (t, J = 8.0 Hz, CDCl3) δ 151.1, 149.2, 140.7, 136.9, 132.2, 130.0, 127.5, 126.92,
1H), 6.90–6.86 (m, 3H), 6.79–6.74 (m, 3H), 6.43 (d, J = 7.5 Hz, 126.89, 126.7, 125.5, 125.0, 119.6, 112.5, 59.3, 44.3, 40.5; MS
2H), 3.77 (s, 2H), 3.72 (s, 3H); 13C NMR (125 MHz, CDCl3) (ESI): 376 [M + H]+; HRMS (ESI) calcd for C28H26N [M + H]+:
δ 159.5, 150.3, 146.3, 140.8, 136.4, 129.9, 129.2, 127.1, 127.0, 376.2065, found: 376.2065.
126.7, 125.6, 124.9, 119.7, 119.4, 113.6, 111.0, 59.9, 55.0, 44.0;
MS (EI, %) m/z 362 (M+, 4), 271 (100); HRMS (EI) calcd for (mixture of two rotamers, syn/anti = 83/17) (syn-rotamer) 1H
C27H22O: 362.1671, found: 362.1670. NMR (500 MHz, CDCl3, TMS) δ 7.73 (d, J = 7.5 Hz, 2H),
Compound 7i: white solid (190.3 mg, 94%); mp: 78–79 °C;
Compound 7c: white solid (266.1 mg, 98%); mp: 7.32–7.28 (m, 2H), 7.23–7.17 (m, 9H), 2.50 (q, J = 7.5 Hz, 2H),
1
142–143 °C; H NMR (300 MHz, CDCl3, TMS) δ 7.44–7.42 (m, 0.41 (t, J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 151.5,
2H), 7.30–7.29 (m, 2H), 7.21–7.19 (m, 6H), 6.84–6.75 (m, 5H), 145.0, 140.9, 128.2, 127.5, 127.3, 127.1, 126.7, 124.3, 119.8,
6.42 (d, J = 7.2 Hz, 2H), 3.73 (s, 2H), 3.68 (s, 3H); 13C NMR 59.2, 30.5; (anti-rotamer) 1H NMR (500 MHz, CDCl3, TMS)
(125 MHz, CDCl3) δ 158.2, 150.8, 140.7, 136.6, 130.0, 127.9, δ 7.78 (d, J = 7.5 Hz, 2H), 7.36–7.33 (m, 2H), 7.23–7.17 (m, 3H),
127.1, 127.0, 126.7, 125.6, 124.9, 119.7, 113.7, 59.3, 55.1, 44.2; 7.14–7.10 (m, 4H), 7.07–7.05 (m, 2H), 2.50 (q, J = 7.5 Hz, 2H),
MS (EI, %) m/z 362 (M+, 2), 271 (100); HRMS (EI) calcd for 0.41 (t, J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 147.8,
C27H22O: 362.1671, found: 362.1673.
141.5, 140.9, 128.6, 128.3, 127.3, 126.8, 126.3, 125.3, 119.8,
Compound 7d: white solid (256.9 mg, 99%); mp: 93–94 °C; 54.4, 8.5; MS (EI, %) m/z 270 (M+, 17), 241 (100); HRMS (EI)
1H NMR (500 MHz, CDCl3, TMS) δ 7.40–7.38 (m, 2H), calcd for C21H18: 270.1409, found: 270.1413.
7.30–7.29 (m, 2H), 7.17–7.16 (m, 4H), 7.11–7.07 (m, 3H), 6.97
Compound 7j: white solid (196.7 mg, 93%); mp: 97–98 °C;
(s, 1H), 6.80 (t, J = 7.5 Hz, 1H), 6.72 (t, J = 7.5 Hz, 2H), 6.40 (d, 1H NMR (500 MHz, CDCl3, TMS) δ 7.71 (d, J = 7.5 Hz, 2H), 7.29
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(dt, J = 7.5, 1.5 Hz, 2H), 7.24–7.10 (m, 9H), 5.23–5.15 (m, 1H), 4H), 7.12 (s, 1H), 7.04 (d, J = 8.5 Hz, 2H), 7.01 (d, J = 7.5 Hz,
4.80 (d, J = 17.0 Hz, 1H), 4.69 (d, J = 10.0 Hz, 1H), 3.20 (d, J = 1H), 6.84 (t, J = 7.5 Hz, 1H), 6.76 (t, J = 8.0 Hz, 2H), 6.43 (d, J =
6.5 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 151.1, 144.2, 140.5, 7.5 Hz, 2H), 3.73 (s, 2H), 2.33 (s, 3H), 2.27 (s, 3H); 13C NMR
133.5, 128.3, 127.4, 127.2, 126.6, 126.4, 124.6, 119.8, 117.8, (125 MHz, CDCl3) δ 150.9, 150.5, 141.7, 140.9, 138.1, 136.8,
58.4, 42.2; MS (EI, %) m/z 282 (M+, 3), 241 (100); HRMS (EI) 136.6, 136.0, 130.0, 129.1, 127.9, 127.0, 126.8, 126.7, 126.5,
calcd for C22H18: 282.1409, found: 282.1411.
Compound 7k:23 white solid (180.5 mg, 94%); (mixture of %) m/z 360 (M+, 3), 269 (100); HRMS (EI) calcd for C28H24:
two rotamers, syn/anti
87/13) (syn-rotamer) 1H NMR 360.1878, found: 360.1880.
(500 MHz, CDCl3, TMS) δ 7.73 (d, J = 7.5 Hz, 2H), 7.34–7.27 Compound 7q: yellow solid (288.8 mg, 99%); mp:
125.6, 125.5, 124.9, 119.4, 119.3, 59.4, 44.0, 21.8, 20.9; MS (EI,
=
1
(m, 2H), 7.20–7.04 (m, 9H), 1.84 (s, 3H); 13C NMR (125 MHz, 145–146 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.40–7.28 (m,
CDCl3) δ 153.8, 144.9, 139.7, 128.2, 127.6, 127.1, 126.4, 126.3, 3H), 7.18–7.14 (m, 5H), 7.01 (d, J = 7.0 Hz, 1H), 6.85 (t, J =
124.0, 120.0, 54.6, 25.2; (anti-rotamer) 1H NMR (500 MHz, 7.0 Hz, 1H), 6.78–6.75 (m, 2H), 6.63 (d, J = 7.0 Hz, 2H), 6.44 (s,
CDCl3, TMS) δ 7.76 (d, J = 7.5 Hz, 2H), 7.34–7.27 (m, 2H), 2H), 3.71 (s, 2H), 2.87 (s, 6H), 2.35 (s, 3H); 13C NMR (125 MHz,
7.20–7.04 (m, 9H), 1.84 (s, 3H); 13C NMR (125 MHz, CDCl3) CDCl3) δ 151.3, 150.9, 149.1, 140.8, 138.1, 137.0, 136.6, 132.4,
δ 147.9, 141.5, 141.0, 128.6, 128.3, 127.3, 126.8, 126.4, 125.3, 130.0, 127.8, 127.5, 126.8, 126.6, 126.4, 125.6, 125.5, 125.0,
119.8, 54.4, 25.2.
119.3, 119.2, 112.5, 59.1, 44.3, 40.5, 21.7; MS (ESI): 390
Compound 7l: yellow solid (202.3 mg, 81%); mp: [M + H]+; HRMS (ESI) calcd for C29H28N [M + H]+: 390.2219,
143–145 °C; 1H NMR (300 MHz, CDCl3, TMS) δ 7.72 (dq, J = found: 390.2222.
4.8, 0.9 Hz, 1H), 7.52–7.43 (m, 4H), 7.27–7.18 (m, 5H),
Compound 7r: white solid (241.3 mg, 93%); mp:
1
7.05–7.01 (m, 1H), 6.90–6.78 (m, 3H), 6.64 (d, J = 7.8 Hz, 1H), 116–117 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.59–7.55 (m,
6.56 (d, J = 6.9 Hz, 2H), 3.98 (s, 2H); 13C NMR (125 MHz, 1H), 7.30–7.29 (m, 1H), 7.25 (d, J = 7.5 Hz, 2H), 7.20–7.12 (m,
CDCl3) δ 162.7, 149.0, 148.9, 140.7, 137.6, 136.1, 130.2, 127.4, 6H), 7.09 (t, J = 7.5 Hz, 1H), 6.96 (d, J = 7.5 Hz, 1H), 6.80 (t, J =
126.9, 126.8, 125.62, 125.57, 121.6, 121.4, 119.8, 62.4, 43.9; MS 7.5 Hz, 1H), 6.72 (t, J = 7.5 Hz, 2H), 6.38 (d, J = 7.5 Hz, 2H),
(EI, %) m/z 333 (M+, 25), 242 (100); HRMS (EI) calcd for 3.75 (s, 2H), 2.44 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 151.03,
C25H19N: 333.1517, found: 333.1512.
151.02, 144.9, 141.9, 138.9, 136.4, 132.6, 129.9, 129.4, 128.3,
Compound 7m: yellow solid (222.3 mg, 89%); mp: 127.0, 126.9, 126.7, 126.6, 126.4, 126.3, 125.6, 124.9, 122.8,
1
181–182 °C; H NMR (300 MHz, CDCl3, TMS) δ 8.72 (d, J = 2.1 122.5, 59.4, 44.1, 20.8; MS (EI, %) m/z 346 (M+, 4), 255 (100);
Hz, 1H), 8.42 (dd, J = 4.5, 1.2 Hz, 1H), 7.46–7.41 (m, 3H), HRMS (EI) calcd for C27H22: 346.1722, found: 346.1726.
7.32–7.21 (m, 6H), 7.07 (dd, J = 8.1, 4.5 Hz, 1H), 6.85 (t, J = 7.2
Compound 7s: white solid (236.9 mg, 84%); mp:
1
Hz, 1H), 6.76 (t, J = 7.2 Hz, 2H), 6.43 (d, J = 7.5 Hz, 2H), 3.78 (s, 137–138 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.58–7.57 (m,
2H); 13C NMR (125 MHz, CDCl3) δ 149.3, 148.3, 147.8, 140.7, 1H), 7.31–7.29 (m, 1H), 7.21–7.09 (m, 6H), 6.98 (d, J = 7.0 Hz,
140.2, 135.6, 134.5, 129.8, 127.5, 127.2, 126.7, 125.8, 124.8, 1H), 6.83 (t, J = 7.5 Hz, 1H), 6.76–6.72 (m, 4H), 6.38 (d, J = 7.5
123.1, 119.8, 58.3, 43.4; MS (EI, %) m/z 333 (M+, 11), 242 (100); Hz, 2H), 3.72 (s, 2H), 3.68 (s, 3H), 2.47 (s, 3H); 13C NMR
HRMS calcd for C25H19N: 333.1517, found: 333.1520.
(125 MHz, CDCl3) δ 158.1, 151.23, 151.21, 141.8, 138.8, 136.9,
Compound 7n: white solid (256.9 mg, 99%); mp: 136.5, 132.6, 129.9, 129.3, 127.9, 126.9, 126.7, 126.6, 126.3,
1
137–138 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.39–7.38 (m, 125.5, 124.8, 122.7, 122.4, 113.6, 58.9, 55.1, 44.4, 20.8; MS (EI,
1H), 7.33–7.14 (m, 9H), 7.11 (s, 1H), 7.01 (d, J = 7.5 Hz, 1H), %) m/z 376 (M+, 2), 285 (100); HRMS calcd for C28H24O:
6.84 (t, J = 7.5 Hz, 1H), 6.76 (t, J = 7.5 Hz, 2H), 6.43 (d, J = 7.0 376.1827, found: 376.1825.
Hz, 2H), 3.75 (s, 2H), 2.32 (s, 3H); 13C NMR (125 MHz, CDCl3)
δ 150.8, 150.4, 144.8, 140.9, 138.2, 136.8, 136.5, 130.0, 128.3, 138–139 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.57–7.55 (m,
128.0, 127.1, 126.9, 126.7, 126.50, 126.46, 125.6, 125.5, 125.0, 1H), 7.31–7.29 (m, 1H), 7.21–7.18 (m, 2H), 7.17–7.14 (m, 3H),
119.43, 119.35, 59.7, 43.9, 21.7; MS (EI, %) m/z 346 (M+, 4), 255 7.10 (t, J = 7.5 Hz, 1H), 7.02 (d, J = 8.0 Hz, 2H), 6.96 (d, J =
Compound 7t: white solid (267.3 mg, 99%); mp:
1
(100); HRMS calcd for C27H22: 346.1722, found: 346.1718.
7.5 Hz, 1H), 6.81 (t, J = 7.5 Hz, 1H), 6.72 (t, J = 7.5 Hz, 2H), 6.38
Compound 7o: white solid (279.2 mg, 99%); mp: (d, J = 7.0 Hz, 2H), 3.73 (s, 2H), 2.45 (s, 3H), 2.25 (s, 3H); 13C
1
134–135 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.42–7.41 (m, NMR (125 MHz, CDCl3) δ 151.17, 151.16, 141.9, 141.8, 138.9,
1H), 7.34 (d, J = 7.5 Hz, 1H), 7.28–7.19 (m, 5H), 7.12 (s, 1H), 136.5, 135.9, 132.6, 129.9, 129.3, 129.0, 127.0, 126.9, 126.8,
7.04 (d, J = 7.5 Hz, 1H), 6.88 (t, J = 7.5 Hz, 1H), 6.81–6.77 (m, 126.7, 126.6, 126.3, 125.5, 124.9, 122.7, 122.4, 59.2, 44.2, 20.9,
4H), 6.43 (d, J = 7.5 Hz, 2H), 3.75 (s, 3H), 3.72 (s, 2H), 2.37 (s, 20.8; MS (EI, %) m/z 360 (M+, 3), 269 (100), 255 (37); HRMS (EI)
3H); 13C NMR (125 MHz, CDCl3) δ 158.1, 151.0, 150.6, 140.8, calcd for C28H24: 360.1878, found: 360.1874.
138.1, 136.8, 136.73, 136.66, 130.0, 127.9, 127.0, 126.7, 126.5,
125.6, 125.5, 124.9, 119.4, 119.3, 113.7, 59.1, 55.1, 44.2, 21.8; 142–143 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.58 (d, J = 5.5
MS (EI, %) m/z 376 (M+, 2), 285 (100); HRMS calcd for Hz, 1H), 7.28–7.12 (m, 7H), 7.00 (s, 1H), 6.90 (t, J = 8.5 Hz, 2H),
Compound 7u: white solid (256.6 mg, 94%); mp:
1
C28H24O: 376.1827, found: 376.1831.
6.83 (t, J = 7.0 Hz, 1H), 6.74 (t, J = 7.0 Hz, 2H), 6.36 (d, J = 7.0
Compound 7p: white solid (259.2 mg, 96%); mp: Hz, 2H), 3.71 (s, 2H), 2.47 (s, 3H); 13C NMR (125 MHz, CDCl3)
1
114–115 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.39–7.37 (m, δ 161.5 (d, JC–F = 243.6 Hz), 150.8 (d, JC–F = 2.9 Hz), 141.8,
1H), 7.31 (d, J = 7.5 Hz, 1H), 7.27–7.25 (m, 1H), 7.19–7.15 (m, 140.6 (d, JC–F = 3.1 Hz), 138.8, 136.2, 132.8, 129.9, 129.5, 128.5
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(d, JC–F = 7.6 Hz), 127.2, 126.8, 126.7, 126.4, 125.7, 124.8, the Key Laboratory of the Ministry of Education for Advanced
122.9, 122.3, 115.0 (d, JC–F = 20.9 Hz), 58.9, 44.3, 20.8; MS (EI, Catalysis Materials (Zhejiang Normal University) (no.
%) m/z 364 (M+, 3), 273 (100); HRMS (EI) calcd for C27H21F: ZJHX201305) is greatly appreciated.
364.1627, found: 364.1629.
Compound 7v: yellow solid (250.9 mg, 86%); mp:
1
142–143 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.60–7.58 (m,
Notes and references
1H), 7.35–7.33 (m, 1H), 7.23–7.11 (m, 6H), 6.99 (d, J = 7.5 Hz,
1H), 6.85 (t, J = 7.5 Hz, 1H), 6.75 (t, J = 7.5 Hz, 2H), 6.64 (d, J =
8.5 Hz, 2H), 6.39 (d, J = 8.5 Hz, 2H), 3.73 (s, 2H), 2.89 (s, 6H),
2.50 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 151.6, 149.1, 141.8,
138.8, 136.9, 132.5, 129.9, 129.1, 127.6, 126.8, 126.6, 126.2,
125.5, 124.9, 122.7, 122.5, 112.5, 58.8, 44.5, 40.5, 20.8; MS
(ESI): 390 [M + H]+; HRMS (ESI) calcd for C29H28N [M + H]+:
390.2213, found: 390.2222.
1 For some recent selected reviews on the transition metal
catalyzed direct C–H bond functionalization, please see:
(a) L. Ackermann, Acc. Chem. Res., 2014, 47, 281;
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Rev., 2013, 42, 5744; (d) F. Shibahara and T. Murai, Asian
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2 For reviews on the NHC–Pd complexes catalyzed coupling
reactions, please see: (a) A. C. Hillier, G. A. Grasa,
M. S. Viciu, H. M. Lee, C.-L. Yang and S. P. Nolan, J. Orga-
nomet. Chem., 2002, 653, 69; (b) E. A. B. Kantchev,
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256, 1787.
Compound 7w: pale yellow solid (259.9 mg, 99%); mp:
1
170–171 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.37–7.19 (m,
10H), 7.02 (dd, J = 7.5, 2.5 Hz, 1H), 6.91–6.85 (m, 2H), 6.78 (t,
J = 7.5 Hz, 2H), 6.44 (d, J = 7.5 Hz, 2H), 3.77 (d, J = 12.5 Hz,
1H), 3.74 (d, J = 12.5 Hz, 1H); 13C NMR (125 MHz, CDCl3)
δ 162.4 (d, JC–F = 243.8 Hz), 152.9 (d, JC–F = 7.5 Hz), 150.5,
143.9, 139.9, 136.8, 136.0, 129.9, 128.5, 127.3, 126.9, 126.81,
126.77, 125.8, 125.0, 120.7 (d, JC–F = 8.8 Hz), 119.4, 114.4 (d,
JC–F = 23.0 Hz), 112.2 (d, JC–F = 22.8 Hz), 60.0, 43.8; MS (EI, %)
m/z 350 (M+, 5), 259 (100); HRMS (EI) calcd for C26H19F:
350.1471, found: 350.1468.
Compound 7x: white solid (270.3 mg, 99%); mp:
1
149–150 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.38–7.29 (m,
3H), 7.21–7.19 (m, 2H), 7.16 (d, J = 8.0 Hz, 2H), 7.06 (d, J = 8.0
Hz, 2H), 7.01 (dd, J = 9.0, 2.5 Hz, 1H), 6.95–6.85 (m, 2H), 6.78
(t, J = 7.5 Hz, 2H), 6.44 (d, J = 7.0 Hz, 2H), 3.75 (d, J = 13.0 Hz,
1H), 3.71 (d, J = 13.0 Hz, 1H), 2.28 (s, 3H); 13C NMR (125 MHz,
CDCl3) δ 162.4 (d, JC–F = 243.9 Hz), 153.0 (d, JC–F = 7.5 Hz),
150.6, 140.9, 139.9, 136.7 (d, JC–F = 2.0 Hz), 136.4, 136.1, 129.9,
129.2, 127.3, 126.8, 126.7, 126.6, 125.8, 124.9, 120.7 (d, JC–F
=
8.8 Hz), 119.4, 114.3 (d, JC–F = 23.0 Hz), 112.2 (d, JC–F = 22.6
Hz), 59.8 (d, JC–F = 1.6 Hz), 44.0, 20.9; MS (EI, %) m/z 364 (M+,
3), 273 (100); HRMS (EI) calcd for C27H21F: 364.1627, found:
364.1628.
3 (a) D. Ghosh and H. M. Lee, Org. Lett., 2012, 14, 5534–5537;
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J. Organomet. Chem., 2011, 696, 2589; (g) İ. Özdemįr,
H. Arslan, S. Demir, D. Vanderveer and B. Çetįnkaya, Inorg.
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İ. Özdemir, B. Çetinkaya, O. Şahin and O. Büyükgüngör,
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4 (a) H.-Y. Yin, M.-Y. Liu and L.-X. Shao, Org. Lett., 2013, 15,
6042; (b) Z.-K. Xiao, H.-Y. Yin and L.-X. Shao, Org. Lett.,
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Compound 7y: yellow solid (268.2 mg, 91%); mp:
1
139–140 °C; H NMR (500 MHz, CDCl3, TMS) δ 7.41–7.31 (m,
3H), 7.24–7.20 (m, 2H), 7.16 (d, J = 9.0 Hz, 2H), 7.03 (dd, J =
9.0, 2.0 Hz, 1H), 6.93–6.87 (m, 2H), 6.79 (t, J = 7.5 Hz, 2H), 6.65
(d, J = 8.0 Hz, 2H), 6.45 (d, J = 8.0 Hz, 2H), 3.74 (d, J = 13.0 Hz,
1H), 3.71 (d, J = 13.0 Hz, 1H), 2.91 (s, 6H); 13C NMR (125 MHz,
CDCl3) δ 162.5 (d, JC–F = 243.5 Hz), 153.5 (d, JC–F = 7.4 Hz),
151.0, 149.4, 139.9, 136.7, 136.5, 131.4, 129.9, 127.4, 127.1,
126.8, 126.6, 125.7, 125.0, 120.6 (d, JC–F = 8.8 Hz), 119.3, 114.1
(d, JC–F = 22.9 Hz), 112.5, 112.2 (d, JC–F = 22.6 Hz), 59.4, 44.3,
40.5; MS (ESI): 394 [M + H]+; HRMS (ESI) calcd for C28H25NF
[M + H]+: 394.1965, found: 394.1971.
Acknowledgements
Financial support from the Open Research Fund of Top Key
Discipline of Chemistry in Zhejiang Provincial Colleges and
This journal is © The Royal Society of Chemistry 2014
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8498 | Org. Biomol. Chem., 2014, 12, 8488–8498
This journal is © The Royal Society of Chemistry 2014