Three-Step Synthesis of Fluoranthenes through Pd-Catalyzed Inter- and Intramolecular C-H Arylation

Article abstract of DOI:10.1021/acs.joc.6b00553

A three-step synthetic method for the preparation of fluoranthenes, involving Miura's intermolecular C-H arylation, nonaflation, and intramolecular C-H arylation, has been developed. Various 1-naphthols and haloarenes were successfully used as substrates. Reaction conditions that afford high site selectivity have been developed for the intramolecular C-H arylation step.

Full text of DOI:10.1021/acs.joc.6b00553

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Note
Three-Step Synthesis of Fluoranthenes through Pd-
Catalyzed Inter and Intramolecular C-H Arylation
Miyuki Yamaguchi, Mayu Higuchi, Kanae Tazawa, and Kei Manabe
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b00553 • Publication Date (Web): 05 Apr 2016
Downloaded from http://pubs.acs.org on April 6, 2016
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Three-Step Synthesis of Fluoranthenes through Pd-Catalyzed Inter and Intramolecular
C−H Arylation
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Miyuki Yamaguchi, Mayu Higuchi, Kanae Tazawa, and Kei Manabe*
School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka
4
22-8526, Japan
Corresponding Author
manabe@u-shizuoka-ken.ac.jp
ABSTRACT: A three-step synthetic method for the preparation of fluoranthenes, involving
Miura’s intermolecular C−H arylation, nonaflation, and intramolecular C−H arylation has been
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developed. Various 1-naphthols and haloarenes were successfully used as substrates. Reaction
conditions that afford high site-selectivity have been developed for the intramolecular C−H
arylation step.
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Polycyclic aromatic hydrocarbons (PAHs) have attracted much attention because of their
1−5
biological, electronic, and optical properties. Fluoranthene is one of the smallest nonalternant
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PAHs, and its framework has often been utilized as a structural motif for many applications, such
6
7
as in sensors and organic field-effect transistors, and as a key synthetic intermediate for
8
,9
bowl-shaped PAHs. While various fluoranthene synthetic methods, many of which utilize
1
0−17
cross-coupling reactions, have been reported,
it is still desirable to develop facile methods for
the synthesis of substituted fluoranthenes from readily available compounds.
Recently, there have been many reports of C−H arylation, especially Pd-catalyzed C−H
arylation with aryl halides, being used to replace conventional cross-coupling reactions to
1
8–20
construct biphenyl units.
Direct arylation at the C−H groups does not require stoichiometric
amounts of pre-formed organometallic compounds, thus making the synthesis of biphenyl
structures easier and more atom-economical. Pd-catalyzed C−H arylation has also been used for
21,22
efficient synthesis of PAHs.
We envisaged that a combination of inter and intramolecular
C−H arylation would help realize a convenient synthetic route to fluoranthenes (Scheme 1). The
first step is the Pd-catalyzed intermolecular C−H arylation of 1-naphthols with halobenzenes.
2
3,24
This reaction, developed by Miura et al.,
site-selectively takes place at the C8 position of
1-naphthols. The second step is nonaflation of the hydroxy group through introduction of a
2
5
2
nonafluorobutanesulfonyl (Nf) group, which is more resistant to O−SO cleavage than the
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commonly used trifluoromethanesulfonyl group.
In addition, the nonaflating agent, NfF, is
generally cheaper than the common triflating agent, Tf
2
O. The third step is the Pd-catalyzed
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intramolecular C−H arylation of the corresponding nonaflates.
This step was designed based
10
on the seminal work of fluoranthene synthesis by Rice and Cai. Herein, we demonstrate the
feasibility of this synthetic scheme, which provides a useful method for fluoranthene synthesis.
Scheme 1. Three-Step Synthesis of Fluoranthenes
Miura’s C−H arylation of 1-naphthols with halobenzenes is a convenient way of
2
3,24
introducing an aryl group at the C8 position.
However, it was only successful with
iodobenzenes; the use of bromobenzenes, which are cheaper and more easily available than
24
iodobenzenes, resulted in poor yields (<5%). To expand the scope of our fluoranthene synthesis,
we first investigated the catalytic conditions of the reaction with bromobenzene. While Miura’s
2 2 3
conditions (Pd(OAc) , Cs CO , DMF) did not afford a significant amount of the desired product,
3
1
3
PCy was found to be effective as a ligand to Pd (Eq. 1). Although the product yield was still
modest, these catalytic conditions significantly expanded the substrate scope of halobenzenes,
and bromobenzenes are now applicable to this C−H arylation.
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Intermolecular C−H arylation of other 1-naphthols 1 and halobenzenes 2 was carried out,
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and various 8-aryl-1-naphthols 3 were obtained (Table 1). Both iodobenzenes and
bromobenzenes were applicable, although the use of bromobenzenes often resulted in lower
yields of 3. Besides 1-naphthol (1a), substituted naphthols 1b and 1c also afforded the
corresponding products in good yields (entries 2 and 3). Halobenzenes substituted at the para-
(entries 4−7) or the meta-positions (entries 8−13) were used. As well as the catalytic system
2 3 2
shown in Eq. 1, PdCl (PCy ) worked well for some bromobenzenes (condition C). Interestingly,
less reactive 3-chloroanisole (2g’) also reacted under catalytic condition C to give 3i, albeit in
low yield (entry 10). Unfortunately, ortho-substituted halobenzenes, such as 2-iodotoluene,
afforded the product only in very low yields (<5%).
Table 1. Intermolecular C−H Arylation of 1-Naphthols with Halobenzenes
a
entry
1
1
2
condition
3
yield (%)
b
A
3a
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C
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3k
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1
3
14
3m
a
2 2 3
A: Pd(OAc) (2.5 mol %), Cs CO (2.0 equiv), DMF, 110 ºC, 19−24 h. B:
Pd(OAc)
2
(10 mol %), PCy
3
(20 mol %), Cs
2
CO
3
(3.6 equiv), DMF, 110 ºC, 24 h.
b
C: PdCl
2
(PCy
3
)
2
(10 mol %), Cs
2
CO
3
(3.6 equiv), DMF, 110 ºC, 18−24 h. This
2
4
combination of 1 and 2 was also reported by Miura et al. The yield shown here
3
2
is based on our experimental results.
3 3
We next performed nonaflation of 3 using NfF and Et N in CH CN (Table 2). Nonaflates 4,
the substrates for the subsequent intramolecular C−H arylation, were successfully obtained in
high yields (81−98%).
Table 2. Nonaflation of 3
entry
3
4
yield (%)
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3k
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3m
4m
We then studied the reaction conditions of another key step, the intramolecular C−H
arylation of nonaflates 4 (Table 3). The initial screening of the catalytic conditions for the
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2 3
intramolecular C−H arylation of 4a led to a combination of Pd (dba) as the Pd source, SPhos
as the ligand, K
3
PO
4
as the base, and DMA as the solvent. Fluoranthene (5a) was obtained in
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good yield (entry 1). To our delight, the use of 1-adamantanecarboxylic acid (1-AdCO
2
H)
as
an additive greatly improved the yield (entry 2). We also tested a meta-substituted substrate 4h to
3
9−45
identify the selectivity between 5b and 6a. Site-selective intramolecular C−H arylation
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proceeded to give 5b as the main product (5b:6a = 50:1, entry 3) probably due to steric effects.
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The use of pivalic acid instead of 1-AdCO H resulted in slight decreases in yield and selectivity
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(
entry 4).
Table 3. Conditions for Intramolecular C−H Arylation
a
entry
1
4
additive
yield (%)
b
4a (R = H)
4a (R = H)
−
<68
2
3
4
1-AdCO
2
2
H
H
98
4h (R = Me) 1-AdCO
4h (R = Me) t-BuCO
91 (50:1)
86 (45:1)
2
H
a
For entries 3 and 4, the products were obtained as a mixture of 5b and
1
6
a. The ratio of 5b to 6a was determined by H NMR and is shown in
b
parentheses. A small amount of impurity was included.
3
4-36
The concerted metalation−deprotonation mechanism
is assumed for the intramolecular
C−H arylation (Scheme 2). The high site-selectivity is attributed to transition state TS, in which
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the sterically less hindered position is involved in the six-membered transition state.
Scheme 2. Assumed mechanism of intramolecular C−H arylation
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With the effective conditions in hand, we applied them to the synthesis of various
substituted fluoranthenes (Table 4). In most cases, good yields were obtained. For fluoranthene
synthesis using meta-substituted substrates (4i−l, entries 7−10), excellent site-selectivities
(>99:1) were observed. Unfortunately, naphthyl-substituted nonaflate 4m gave
benzo[k]fluoranthene (5j) in lower yield and selectivity under these conditions (entry 11).
Table 4. Intramolecular C−H Arylation of Nonaflates
a
entry
4
5
yield (%)
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84
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4g
4i
9
2
(
(
(
>99:1)
8
0
4j
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4k
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4l
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>99:1)
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b
4m
(
8)
a
1
The ratio of the isomers was determined by H NMR
b
and is shown in parentheses. Yield of 6b.
In conclusion, we developed a strategy for the three-step synthesis of fluoranthenes
consisting of Pd-catalyzed inter and intramolecular C−H arylation. Fluoranthenes were produced
in acceptable yields without using stoichiometric amounts of organometallic reagents. Various
1
-naphthols and halobenzenes, including bromobenzenes, were successfully used as the starting
materials. While only mono-substituted fluoranthenes were synthesized in this work, this
three-step procedure is expected to be easily applied to the synthesis of multi-substituted
fluoranthenes. Considering the wide availability of 1-naphthols and halobenzenes together with
the highly site-selective intramolecular C−H arylation step, this synthetic method will provide a
useful route to various fluoranthenes. Furthermore, the strategy could be applied to the synthesis
of other PAHs.
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EXPERIMENTAL SECTION:
All reactions were conducted under an argon atmosphere. All of the starting materials,
catalysts, and reagents are commercially available and were used as purchased without further
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3
purification. DMF, CH CN, and DMA were purchased as anhydrous solvents. Melting points are
1
uncorrected. For H NMR, tetramethylsilane (TMS) (δ = 0) in CDCl
3
was used as the internal
1
3
46
3
standard. For C NMR, CDCl (δ = 77.0) served as an internal standard. Compounds 1b and
4
7,48
1
c
were prepared according to procedures reported in the literature.
2
4
General procedure for intermolecular C−H arylation (condition A). To a suspension
2 3 2
of 1-naphthol, Cs CO (2 equiv), and Pd(OAc) (2.5 mol %) in DMF (5.0 mL/1 mmol
1-naphthol) was added an iodoarene (1.2 equiv) at rt. The mixture was heated at 110 ºC and
stirred for 19−24 h. After cooling to rt, the mixture was diluted with EtOAc, washed with 1 M aq.
2 4
HCl, water, and brine, dried over Na SO , and concentrated under vacuum. Purification by
chromatography gave the desired product.
General procedure for intermolecular C−H arylation (condition B). To a suspension of
2 3 2 3
1-naphthol, Cs CO (3.6 equiv), Pd(OAc) (10 mol %), and PCy (20 mol %) in DMF (8.0 mL/1
mmol 1-naphthol) was added a bromoarene (1.2 equiv) at rt. The mixture was heated at 110 ºC
and stirred for 24 h. After cooling to rt, the mixture was diluted with EtOAc, washed with 1 M aq.
HCl, water, and brine, dried over Na
2
SO
4
, and concentrated under vacuum. Purification by
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chromatography gave the desired product.
General procedure for intermolecular C−H arylation (condition C). To a suspension of
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
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0
1-naphthol, Cs
2 3 2 3 2
CO (3.6 equiv), and PdCl (PCy ) (10 mol %) in DMF (8.0 mL/1 mmol
1-naphthol) was added a bromoarene (1.2 equiv) at rt. The mixture was heated at 110 ºC and
stirred for 18−24 h. After cooling to rt, the mixture was diluted with EtOAc, washed with 1 M aq.
2 4
HCl, water, and brine, dried over Na SO , and concentrated under vacuum. Purification by
chromatography gave the desired product.
2
4
8-Phenylnaphthalen-1-ol (3a) (Eq. 1 and Table 1, entry 1). 1-Naphthol (1a) (72.1 mg,
0.50 mmol) was subjected to the intermolecular C−H arylation under condition B for 24 h. After
2 2 3
column chromatography twice (SiO , hexane/EtOAc = 100/1−25/1 and SiO , hexane/CHCl =
2
0
0/1), 3a (45.6 mg, 41%) was obtained as a yellow oil. Alternatively, 1-naphthol (1a) (72.1 mg,
.50 mmol) was subjected to the intermolecular C−H arylation under conditions A for 19 h. After
2
column chromatography (SiO , hexane/EtOAc = 100/1−40/1), 3a (51.2 mg, 47%) was obtained
1
as a yellow oil. H NMR (400 MHz, CDCl
3
): δ 5.41 (1H, s), 6.92 (1H, dd, J = 1.5, 7.3 Hz), 7.21
(1H, dd, J = 1.5, 7.3 Hz), 7.40 (1H, t, J = 7.8 Hz), 7.44 (1H, t, J = 8.3 Hz), 7.49−7.51 (6H, m),
1
3
1
7
1
.86 (1H, dd, J = 1.5, 8.3 Hz) ppm; C{ H} NMR (100 MHz, CDCl
3
): δ 111.8, 121.0, 121.3,
24.2, 126.8, 128.5, 128.6, 128.7, 128.9, 129.4, 135.7, 136.1, 141.3, 153.0 ppm.
5-Methoxy-8-phenylnaphthalen-1-ol (3b) (Table 1, entry 2). Naphthol 1b (256 mg, 1.5
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mmol) was subjected to the intermolecular C−H arylation under condition A for 24 h. After
column chromatography (SiO
2
, hexane/EtOAc = 100/1−40/1), 3b (289 mg, 77%) was obtained as
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
a brown solid. Mp. 95.3−96.8 ºC; H NMR (400 MHz, CDCl
3
): δ 4.03 (3H, s), 5.44 (1H, s), 6.81
(
1H, d, J = 8.0 Hz), 6.94 (1H, d, J = 7.6 Hz), 7.11 (1H, d, J = 7.6 Hz), 7.40 (1H, t, J = 8.0),
1
3
1
7
1
.44−7.54 (5H, m), 7.96 (1H, d, J = 8.0 Hz) ppm; C{ H} NMR (100 MHz, CDCl
3
): δ 55.6,
03.0, 112.6, 114.6, 122.0, 126.3, 127.5, 128.26, 128.28, 128.4, 128.9, 129.8, 141.4, 152.9, 155.4
−
1
ppm; IR (ATR) 615, 698, 750, 1042, 1244, 3429, 3472 cm ; HRMS (DART-TOF): m/z calcd for
+
C
17
H
15
O
2
([M+H] ) 251.1067; found: 251.1079.
6-Methoxy-8-phenylnaphthalen-1-ol (3c) (Table 1, entry 3). Naphthol 1c (321 mg, 1.4
mmol) was subjected to the intermolecular C−H arylation under condition A for 24 h. After
column chromatography (SiO
2
2
, hexane/EtOAc = 100/1−40/1) and preparative TLC twice (SiO ,
1
hexane/EtOAc = 8/1 and 4/1), 3c (183 mg, 51%) was obtained as a yellow oil. H NMR (400
3
MHz, CDCl ): δ 3.95 (3H, s), 5.33 (1H, s), 6.77 (1H, d, J = 6.8 Hz), 6.90 (1H, d, J = 2.4 Hz),
13
1
7
3
.18 (1H, d, J = 2.4 Hz), 7.32-7.45 (2H, m), 7.52 (5H, s) ppm; C{ H} NMR (100 MHz, CDCl ):
δ 55.3, 106.6, 109.8, 116.9, 119.9, 120.9, 127.6, 128.7, 129.0, 129.3, 137.3, 138.0, 140.9, 153.3,
−
1
1
56.2 ppm; IR (ATR): 602, 619, 768, 812, 1458, 2926, 2963, 3044 cm ; HRMS (DART-TOF):
+
m/z calcd for C17
H
15
O
2
([M+H] ) 251.1067; found: 251.1074.
8
-(4-Methoxyphenyl)naphthalen-1-ol (3d) (Table 1, entry 4). 1-Naphthol (1a) (145 mg,
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1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
.0 mmol) was subjected to the intermolecular C−H arylation under condition A for 24 h. After
column chromatography (SiO
2
, hexane/EtOAc = 100/1−40/1), 3d (100 mg, 40%) was obtained as
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
a yellow solid. Mp. 114.1−114.9 ºC; H NMR (400 MHz, CDCl
3
): δ 3.91 (3H, s), 5.73 (1H, s),
6
7
1
.96 (1H, d, J = 7.8 Hz), 7.07 (2H, d, J = 8.3 Hz), 7.22 (1H, t, J = 6.8), 7.39−7.50 (4H, m),
1
3
1
3
.50−7.58 (1H, m), 7.88 (1H, d, J = 8.3 Hz) ppm; C{ H} NMR (100 MHz, CDCl ): δ ppm 55.3,
11.6, 114.4, 120.8, 121.5, 124.8, 126.8, 128.5, 128.7, 130.7, 133.0, 135.7, 135.8, 153.2, 159.8
−
1
ppm; IR (ATR): 563, 768, 827, 1177, 1233, 3460 cm ; HRMS (DRAT-TOF): m/z calcd for
+
C
17
H
15
O
2
([M+H] ) 251.1067; found: 251.1083.
8-(4-(Trifluoromethyl)phenyl)naphthalen-1-ol (3e) (Table 1, entry 5). 1-Naphthol (1a)
(72.2 mg, 0.50 mmol) was subjected to the intermolecular C−H arylation under condition A for
2
4 h. After column chromatography (SiO
2
2
, hexane/EtOAc = 100/1) and preparative TLC (SiO ,
1
hexane/CH
2
Cl
2
= 1/1), 3e (70.9 mg, 49%) was obtained as a white solid. Mp. 72.8−74.0 ºC; H
3
NMR (400 MHz, CDCl ): δ 5.02 (1H, s), 5.91 (1H, d, J = 7.8 Hz), 7.23 (1H, d, J = 6.8 Hz), 7.43
(1H, t, J = 8.1 Hz), 7.50 (1H, t, J = 7.5 Hz), 7.57 (1H, d, J = 8.3 Hz) , 7.63 (2H, d, J = 7.8 Hz),
13
1
7
1
1
1
3
.76 (2H, d, J = 8.3 Hz), 7.92 (1H, d, J = 8.3 Hz) ppm; C{ H} NMR (100 MHz, CDCl ): δ
1
3
12.0, 121.2, 121.5, 124.1 (q, JCF = 272.0 Hz), 125.0, 125.3 (q, JCF = 3.3 Hz), 126.9, 128.8,
2
29.1, 129.8, 130.1 (q, JCF = 33.0 Hz), 135.4, 135.8, 146.2, 152.4 ppm; IR (ATR): 615, 758, 820,
−
1
+
12 3
061, 1074, 1107, 1321, 3051 cm ; HRMS (DART-TOF): m/z calcd for C17H F O ([M+H] )
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89.0835; found: 289.0837.
-(4-Methylphenyl)naphthalen-1-ol (3f) (Table 1, entry 6). 1-Naphthol (1a) (72.2 mg,
.50 mmol) was subjected to the intermolecular C−H arylation under condition B for 24 h. After
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
8
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
0
column chromatography (SiO
2
, hexane/EtOAc = 100/1−40/1, and then NH Silica, hexane/CHCl
3
1
=
20/1−10/1), 3f (39.9 mg, 32%) was obtained as a yellow solid. Mp. 81.4−83.1 ºC; H NMR
3
(400 MHz, CDCl ): δ 2.48 (3H, s), 5.59 (1H, s), 6.93 (1H, d, J = 7.3 Hz), 7.21 (1H, d, J = 6.8 Hz),
7
.35 (2H, d, J = 8.0 Hz), 7.39−7.49 (4H, m), 7.52 (1H, d, J = 8.3 Hz), 7.87 (1H, d, J = 8.3 Hz)
1
3
1
3
ppm; C{ H} NMR(100 MHz, CDCl ): δ 21.3, 111.7, 120.9, 121.4, 124.8, 126.8, 128.5, 128.6,
129.3, 129.7, 135.7, 136.2, 138.2, 138.6, 153.2 ppm; IR (ATR): 617, 764, 820, 1233, 1389, 3478
−
1
+
cm ; HRMS (DART-TOF): m/z calcd for C17
-(4-Ethylphenyl)naphthalen-1-ol (3g) (Table 1, entry 7). 1-Naphthol (1a) (144 mg, 1.0
mmol) was subjected to the intermolecular C−H arylation under condition B for 24 h. After
H15O ([M+H] ) 235.1117; found: 235.1116.
8
2 3
column chromatography (SiO , hexane/EtOAc = 100/1−50/1, and then NH Silica, hexane/CHCl
=
2 3
1/0−10/1) and preparative TLC (SiO , hexane/CHCl = 1/1), 3g (32.2 mg, 18%) was obtained
1
as a yellow oil. H NMR (400 MHz, CDCl
3
): δ 1.33 (3H, t, J = 7.6 Hz), 2.77 (2H, q, J = 7.3 Hz),
5
.99 (1H, s), 6.92 (1H, d, J = 7.8 Hz), 7.21 (1H, d, J = 6.8 Hz), 7.32−7.48 (6H, m), 7.51 (1H, d, J
1
3
1
=
7.8 Hz), 7.86 (1H, d, J = 8.3 Hz) ppm; C{ H} NMR (100 MHz, CDCl
3
): δ 15.4, 28.6, 111.7,
1
20.9, 121.4, 124.8, 126.8, 128.47, 128.50, 128.6, 129.4, 135.7, 136.2, 138.3, 144.9, 153.2 ppm;
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1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
−
1
17
IR (ATR): 764, 819, 1233, 1389, 1454, 3497 cm ; HRMS (DART-TOF): m/z calcd for C18H O
+
(
[M+H] ) 249.1274; found: 249.1278.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
8
-(3-Methylphenyl)naphthalen-1-ol (3h) (Table 1, entry 8). 1-Naphthol (1a) (721 mg,
5
.0 mmol) was subjected to the intermolecular C−H arylation under condition A for 24 h. After
2
column chromatography (SiO , hexane/EtOAc = 100/1−50/1), 3h (761 mg, 65%) was obtained as
1
a yellow oil. H NMR (400 MHz, CDCl
3
): δ 2.43 (3H, s), 5.54 (1H, s), 6.91 (1H, dd, J =1.2, 7.6
Hz), 7.19 (1H, dd, J =1.2, 7.1 Hz), 7.32−7.44 (4H, m), 7.49 (1H, dd, J =1.2, 8.0Hz), 7.84 (1H, dd,
1
3
1
3
J = 8.3, 1.0 Hz) ppm; C{ H} NMR (100 MHz, CDCl ): δ 21.4, 111.7, 120.9, 121.3, 124.7,
126.4, 126.8, 128.2, 128.6, 128.8, 129.3, 130.1, 125.7, 136.2, 138.8, 141.2, 153.1 ppm; IR
-
1
13
(ATR): 712, 764, 822, 1186, 1233, 1387, 3497 cm ; HRMS (ESI-TOF): m/z calcd for C17H O
−
(
[M−H] ) 233.0972; found: 233.0974.
8
-(3-Methoxyphenyl)naphthalen-1-ol (3i) (Table 1, entries 9 and 10). 1-Naphthol (1a)
(
72.2 mg, 0.50 mmol) was subjected to the intermolecular C−H arylation under condition A for
2
2
4 h. After column chromatography (SiO , hexane/EtOAc = 100/1−20/1), 3i (70.1 mg, 56%) was
obtained as a yellow oil. Alternatively, 1-naphthol (1a) (72.1 mg, 0.50 mmol) was subjected to
the intermolecular C−H arylation under conditions C for 24 h. After column chromatography
2 3
three times (SiO , hexane/EtOAc = 100/1, NH Silica, hexane/CHCl = 10/3, and NH Silica,
3 2
hexane/CHCl = 10/1) and preparative TLC (SiO , hexane/EtOAc = 3/1), 3i (16.2 mg, 13%) was
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obtained as a yellow oil. H NMR (400 MHz, CDCl ): δ 3.85 (3H, s), 5.58 (1H, s), 6.92 (1H, dd,
J = 7.3, 1.0), 7.03−7.09 (3H, m), 7.22 (1H, dd, J = 6.8, 1.5 Hz), 7.38−7.46 (3H, m), 7.50 (1H, dd,
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
13
1
3
J = 8.0, 1.5), 7.86 (1H, dd, J = 8.3, 1.5 Hz) ppm; C{ H} NMR (100 MHz, CDCl ): δ 55.4, 111.9,
1
1
14.5, 114.8, 121.0, 121.3, 121.5, 124.8, 126.9, 128.2, 128.8, 130.1, 135.6, 136.0, 142.7, 153.0,
−
1
59.7 ppm; IR (ATR): 708, 766, 822, 1038, 1219, 1578, 2942, 3482 cm ; HRMS (DART-TOF):
+
m/z calcd for C17
H
15
O
2
([M+H] ) 251.1067; found: 251.1078.
8
-(3-(Trifluoromethyl)phenyl)naphthalen-1-ol (3j) (Table 1, entry 11). 1-Naphthol (1a)
(72.3 mg, 0.50 mmol) was subjected to the intermolecular C−H arylation under condition A for
24 h. After column chromatography (SiO
2
, hexane/EtOAc = 100/1−30/1) and preparative TLC
1
(SiO
2
, hexane/CHCl
3
= 1/1), 3j (61.7 mg, 43%) was obtained as a yellow oil. H NMR (400 MHz,
3
CDCl ): δ 4.97 (1H, s), 6.90 (1H, d, J = 7.3 Hz), 7.24 (1H, d, J = 6.8 Hz), 7.42 (1H, t, J = 8.0 Hz),
7
7
.49 (1H, t, J = 7.6 Hz), 7.55 (1H, d, J = 7.8 Hz), 7.58−7.66 (1H, m), 7.70 (1H, d, J = 4.0 Hz),
13
1
.74 (1H, d, J = 8.0 Hz), 7.79 (1H, s), 7.91 (1H, d, J = 8.2 Hz) ppm; C{ H} NMR (100 MHz,
1
3
CDCl
3
): δ 111.9, 121.1, 121.3, 124.5 (q, JCF = 273.1 Hz), 124.7 (q, JCF = 4.0 Hz), 125.1, 126.3
3
2
(
q, JCF = 4.0 Hz), 126.9, 128.8, 129.0, 129.2, 130.7 (q, JCF = 32.1 Hz), 132.7, 135.4, 135.9,
−
1
1
43.3, 152.5 ppm; IR (ATR): 507, 704, 766, 1067, 1096, 1119, 1161, 3049, 3539 cm ; HRMS
+
(DART-TOF): m/z calcd for C17
H
12
F
3
O ([M+H] ) 289.0835; found: 289.0851.
8
-(3-Isopropylphenyl)naphthalen-1-ol (3k) (Table 1, entry 12). 1-Naphthol (1a) (72.1
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1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
mg, 0.50 mmol) was subjected to the intermolecular C−H arylation under condition C for 18 h.
After column chromatography (SiO
2
2
, hexane/EtOAc = 100/1) and preparative TLC (SiO ,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
hexane/EtOAc = 8/1), 3k (48.7 mg, 37%) was obtained as a yellow oil. H NMR (400 MHz,
3
CDCl ): δ 1.33 (6H, d, J = 6.8 Hz), 3.01 (1H, spt, J = 6.8 Hz), 5.60 (1H, s), 6.95 (1H, dd, J = 7.3
1
.0 Hz), 7.25 (1H, dd, J = 6.8, 1.0 Hz), 7.32−7.51 (6H, m), 7.53 (1H, d, J = 7.8 Hz), 7.89 (1H, d,
1
3
1
3
J = 7.8 Hz) ppm; C{ H} NMR (100 MHz, CDCl ): δ 23.9, 34.1, 111.7, 120.9, 121.3, 124.8,
1
26.76, 126.82, 126.84, 127.5, 128.3, 128.6, 129.0, 135.7, 136.5, 141.2, 149.8, 153.2 ppm; IR
−
1
17
(ATR): 712, 766, 826, 1233, 1389, 2959, 3497 cm ; HRMS (ESI-TOF): m/z calcd for C19H O
−
([M−H] ) 261.1274; found: 261.1277.
8-(3-(N,N-Dimethylamino)phenyl)naphthalen-1-ol (3l) (Table 1, entry 13). 1-Naphthol
1a) (72.1 mg, 0.50 mmol) was subjected to the intermolecular C−H arylation under condition C
(
2
for 24 h. After column chromatography (SiO , hexane/EtOAc = 100/1−40/1), 3l (50.4 mg, 38%)
1
3
was obtained as a yellow oil. H NMR (400 MHz, CDCl ): δ 2.97 (6H, s), 5.97 (1H, s), 6.76−6.83
(3H, m), 6.91 (1H, d, J = 8.0 Hz), 7.24 (1H, dd, J = 8.0, 4.0 Hz), 7.35 (1H, t, J = 6.0), 7.46 (1H, d,
J = 8.0), 7.42 (1H, d, J = 8.0), 7.48 (1H, d, J = 8.0 Hz), 7.84 (1H, dd, J = 8.0, 6.0 Hz) ppm;
1
3
1
3
C{ H} NMR (100 MHz, CDCl ): δ 40.3, 111.7, 112.3, 112.8, 116.8, 120.7, 121.4, 124.8, 126.8,
1
1
27.9, 128.5, 129.8, 135.6, 137.1, 142.1, 150.5, 153.4 ppm; IR (ATR): 422, 455, 492, 706, 764,
−
1
+
234, 1593, 3460 cm ; HRMS (DRAT-TOF): m/z calcd for C18H18NO ([M+H] ) 264.1383;
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found: 264.1388.
1,2’-Binaphthalen]-8-ol (3m) (Table 1, entry 14). 1-Naphthol (1a) (72.1 mg, 0.50 mmol)
was subjected to the intermolecular C−H arylation under condition B for 24 h. After column
[
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
chromatography (SiO
2
2 3
, hexane/EtOAc = 100/1) and preparative TLC (SiO , hexane/CHCl = 1/1),
1
3
6
7
m (58.5 mg, 43%) was obtained as a yellow solid. H NMR (400 MHz, CDCl
3
): δ 5.48 (1H, s),
.93 (1H, d, J = 7.3 Hz), 7.30 (1H, d, J = 7.3 Hz),7.39−7.46 (1H, m), 7.49 (1H, t, J = 7.6 Hz),
1
3
1
.51 (1H, d, J = 8.3), 7.58−7.66 (3H, m), 7.88−7.93 (2H, m), 7.94−8.04 (3H, m) ppm; C{ H}
3
NMR (100 MHz, CDCl ): δ 111.8, 121.1, 121.5, 124.9, 126.8, 126.9, 127.1, 127.3, 127.9, 128.2,
128.6, 128.76, 128.83, 132.9, 133.0, 135.8, 136.2, 138.9, 153.1 ppm (One carbon signal is
−
1
overlapped.); IR (ATR): 741, 756, 818, 1260, 1325, 1580, 3530 cm ; HRMS (DART-TOF): m/z
+
calcd for C20
H15O ([M+H] ) 271.1117; found: 271.1126.
3
General procedure for nonaflation. To a solution of an 8-aryl-1-naphthol in CH CN (2.6
3
mL/1 mmol 8-aryl-1-naphthol) was added Et N (3.3 equiv) at rt. After cooling to 0 ºC, NfF
(1.3−6.5 equiv) was added dropwise for 1 min. The reaction mixture was allowed to warm to rt
and was then stirred for 3−13 h, after which 1 M aq. HCl was added. The mixture was extracted
with EtOAc, washed with water and brine, dried over Na
Purification by chromatography gave the desired product.
2 4
SO , and concentrated under vacuum.
8-Phenylnaphthalen-1-yl nonafluorobutanesulfonate (4a) (Table 2, entry 1). Naphthol
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2
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6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
3
a (110 mg, 0.50 mmol) was subjected to the nonaflation with 1.3 equiv of NfF for 4 h. After
column chromatography twice (SiO
2
, hexane/EtOAc = 100/1−40/1 and hexane/EtOAc = 100/1),
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
4
a (211 mg, 84%) was obtained as a pale yellow solid. Mp.77.7−78.5 ºC; H NMR (400 MHz,
3
CDCl ): δ 7.38−7.50 (8H, m), 7.60 (1H, t, J = 7.6 Hz), 7.92 (1H, dd, J = 8.3, 1.0 Hz), 7.97 (1H,
1
3
1
3
dd, J = 8.3, 1.0 Hz); C{ H} NMR (100 MHz, CDCl ): δ 119.7, 124.5, 125.0, 126.5, 127.4,
1
27.8, 128.0, 129.6, 129.7, 132.2, 136.3, 137.4, 161.6, 146.0 ppm (The perfluorobutyl carbons
−
1
were not observed.); IR (ATR): 527, 563, 588, 696, 764, 1140, 1192 cm ; HRMS (DART-TOF):
+
m/z calcd for C20
H
12
F
9
O
3
S ([M+H] ) 503.0358; found: 503.0344.
5-Methoxy-8-phenylnaphthalen-1-yl nonafluorobutanesulfonate (4b) (Table 2, entry
2). Naphthol 3b (228 mg, 0.91 mmol) was subjected to the nonaflation with 1.3 equiv of NfF for
5
h. After column chromatography twice (SiO
2
, hexane/EtOAc = 50/1), 4b (475 mg, 98%) was
1
obtained as a yellow solid. Mp. 107.8−109.7 ºC; H NMR (400 MHz, CDCl
3
): δ 4.07 (3H, s),
13
1
6.97 (1H, d, J = 8.3 Hz), 7.31−7.69 (8H, m), 8.49 (1H, dd, J = 7.3, 2.0 Hz ) ppm; C{ H} NMR
3
(100 MHz, CDCl ): δ 55.8, 104.7, 120.3, 123.5, 124.3, 125.4, 127.0, 127.7, 128.3, 129.4, 129.8,
1
5
32.3, 141.8, 145.9, 154.7 ppm (The perfluorobutyl carbons were not observed.); IR (ATR): 511,
−
1
14 9 4
71, 733, 766, 1020, 1140, 1194, 1425 cm ; HRMS (DART-TOF): m/z calcd for C21H F O S
+
([M+H] ) 533.0464; found: 533.0459.
6-Methoxy-8-phenylnaphthalen-1-yl nonafluorobutanesulfonate (4c) (Table 2, entry 3).
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2
3
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5
6
7
8
9
Naphthol 3c (227 mg, 0.91 mmol) was subjected to the nonaflation with 1.3 equiv of NfF for 7 h.
After preparative TLC three times (SiO
2
, hexane/EtOAc = 8/1, hexane/CH
2
Cl
2
= 1/1 twice), 4c
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
(
393 mg, 81%) was obtained as a pale yellow solid. Mp. 111.3−112.2 ºC; H NMR (400 MHz,
3
CDCl ): δ 3.97 (3H, s), 7.19 (1H, d, J = 2.4 Hz), 7.23 (1H, d, J = 2.4 Hz), 7.31 (1H, d, J = 7.8
1
3
1
3
Hz), 7.39−7.52 (6H, m), 7.85 (1H, d, J = 8.3 Hz) ppm; C{ H} NMR (100 MHz, CDCl ): δ 55.4,
1
06.1, 117.2, 120.1, 124.5, 125.6, 127.5, 127.8, 128.3, 129.5, 138.0, 139.3, 141.2, 146.3, 157.4
ppm (The perfluorobutyl carbons were not observed.); IR (ATR): 563, 839, 1003, 1136, 1177,
−
1
+
14 9 4
1192, 1425 cm ; HRMS (DART-TOF): m/z calcd for C21H F O S ([M+H] ) 533.0464; found:
533.0487.
8-(4-Methoxyphenyl)naphthalen-1-yl nonafluorobutanesulfonate (4d) (Table 2, entry
4
). Naphthol 3d (83.3 mg, 0.33 mmol) was subjected to the nonaflation with 1.3 equiv of NfF for
7
h. After preparative TLC (SiO
2
, hexane/EtOAc = 5/1), 4d (159 mg, 90%) was obtained as a
1
pale yellow solid. Mp. 115.4−116.7 ºC; H NMR (400 MHz, CDCl
3
): δ 3.89 (3H, s), 7.01 (2H, d,
J = 8.7 Hz), 7.36 (2H, d, J = 8.7 Hz), 7.43−7.56 (3H, m), 7.60 (1H, t, J = 7.8 Hz), 7.91 (1H, d, J
13
1
=
3
7.8 Hz), 7.97 (1H, d, J = 7.8 Hz) ppm; C{ H} NMR (100 MHz, CDCl ): δ 55.3, 113.4, 119.8,
1
24.7, 124.9, 126.5, 127.6, 129.7, 130.8, 132.1, 134.1, 136.4, 137.2, 146.0, 159.4 ppm (The
perfluorobutyl carbons were not observed.); IR (ATR): 561, 584, 766, 820, 1136, 1180, 1242
−
1
+
14 9 4
cm ; HRMS (DART-TOF): m/z calcd for C21H F O S ([M+H] ) 533.0464; found: 533.0453.
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2
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7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
8
-(4-(Trifluoromethyl)phenyl)naphthalen-1-yl nonafluorobutanesulfonate (4e) (Table
2
, entry 5). Naphthol 3e (199 mg, 0.69 mmol) was subjected to the nonaflation with 1.3 equiv of
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2
NfF for 7 h. After preparative TLC twice (SiO , hexane/EtOAc = 8/1 twice) and column
2 2 2
chromatography (SiO , hexane/CH Cl = 1/0−20/1), 4e (387 mg, 98%) was obtained as a pale
1
3
yellow solid. Mp. 108.1−108.9 ºC; H NMR (400 MHz, CDCl ): δ 7.48−7.60 (5H, m), 7.64 (1H, t,
1
3
1
J = 7.6 Hz), 7.72 (2H, d, J = 8.3 Hz), 8.00 (2H, t, J = 7.3 Hz) ppm; C{ H} NMR (100 MHz,
1
3
CDCl
3
): δ 120.1, 124.35, 124.39 (q, JCF = 270.8 Hz), 124.8 (q, JCF = 4.2 Hz), 125.4, 126.5,
2
128.7, 129.2, 129.86 (q, JCF = 23.1 Hz), 129.90, 132.0, 135.9, 136.3, 145.3, 145.4 ppm (The
−
1
perfluorobutyl carbons were not observed.); IR (ATR): 727, 764, 826, 1136, 1323, 1431 cm ;
＋
·
10 12 3
HRMS (DART-TOF): m/z calcd for C21H F O S (M ) 570.0154; found: 570.0186.
8-(4-Methylphenyl)naphthalen-1-yl nonafluorobutanesulfonate (4f) (Table 2, entry 6).
Naphthol 3f (47.8 mg, 0.20 mmol) was subjected to the nonaflation with 1.3 equiv of NfF for 7 h.
After preparative TLC twice (SiO
2
, hexane/EtOAc = 8/1, hexane/EtOAc = 5/1), 4f (90.8 mg,
1
8
6%) was obtained as a pale yellow solid. Mp. 97.1−98.1 ºC; H NMR (400 MHz, CDCl
3
): δ 2.46
(
3H, s), 7.28 (2H, d, J = 8.0 Hz), 7.33 (2H, d, J = 8.0 Hz), 7.44−7.57 (3H, m), 7.61 (1H, t, J = 7.6
1
3
1
3
Hz), 7.92 (1H, d, J = 7.8 Hz), 7.99 (1H, d, J = 4.0 Hz) ppm; C{ H} NMR (100 MHz, CDCl ): δ
2
1
1.1, 119.8, 124.7, 124.9, 126.5, 127.7, 128.5, 129.5, 129.6, 132.1, 136.3, 137.2, 137.5, 138.7,
46.0 ppm (The perfluorobutyl carbons were not observed.); IR (ATR): 571, 764, 814, 1136,
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2
3
4
−
1
+
1
14 9 3
188, 1431 cm ; HRMS (DART-TOF): m/z calcd for C21H F O S ([M+H] ) 517.0514; found:
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
5
17.0502.
-(4-Ethylphenyl)naphthalen-1-yl nonafluorobutanesulfonate (4g) (Table 2, entry 7).
Naphthol 3g (33.7 mg, 0.14 mmol) was subjected to the nonaflation with 1.3 equiv of NfF for 7 h.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
8
After preparative TLC (SiO
2
3
, hexane/CHCl = 2/1), 4g (67.6 mg, 94%) was obtained as a pale
1
yellow solid. Mp. 111.1−112.2 ºC; H NMR (400 MHz, CDCl
3
): δ 1.31 (3H, t, J = 7.8 Hz), 2.75
(2H, q, J = 7.8 Hz), 7.31 (4H, m), 7.47 (1H, d, J = 8.0 Hz), 7.52 (2H, t, J = 8.0 Hz), 7.60 (1H, t, J
1
3
1
= 8.0 Hz), 7.92 (1H, d, J = 8.3 Hz), 7.97 (1H, d, J = 7.8 Hz) ppm; C{ H} NMR (100 MHz,
3
CDCl ): δ 15.6, 28.7, 119.7, 124.7, 124.9, 126.5, 127.3, 127.7, 129.55, 129.57, 132.0, 136.3,
137.6, 138.9, 143.6, 145.8 ppm (The perfluorobutyl carbons were not observed.); IR (ATR): 569,
−
1
6
98, 725, 764, 824, 1136, 1186, 1204, 1431 cm ; HRMS (DART-TOF): m/z calcd for
+
C
22
H
16
F
9
O
3
S ([M+H] ) 531.0671; found: 531.0659.
8-(3-Methylphenyl)naphthalen-1-yl nonafluorobutanesulfonate (4h) (Table 2, entry 8).
Naphthol 3h (116 mg, 0.50 mmol) was subjected to the nonaflation with 2.0 equiv of NfF for 8 h.
2
After preparative TLC (SiO , hexane/EtOAc = 8/1), 4h (240 mg, 94%) was obtained as a yellow
1
solid. Mp. 55.6−56.9 ºC; H NMR (400 MHz, CDCl
3
): δ 2.41 (3H, s), 7.22 (3H, m), 7.34 (1H, t, J
=
3.8, 8.0 Hz), 7.48 (3H, m), 7.56 (1H, t, J = 7.8, 8.0 Hz), 7.88 (1H, dd, J = 1.6, 8.4 Hz) , 7.92
1
3
1
3
(1H, t, J = 4.3, 4.6 Hz) ppm; C{ H} NMR (100 MHz, CDCl ): δ 21.3, 119.6, 124.6, 124.9,
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7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
26.5, 126.7, 127.7, 127.9, 128.0, 130.0, 130.4, 132.0, 136.3, 137.4, 137.6, 141.6, 146.0 ppm
(The perfluorobutyl carbons were not observed.); IR (ATR): 569, 583, 762, 1126, 1140, 1192,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
−1
+
1
5
14 9 3
425 cm ; HRMS (DART-TOF): m/z calcd for C21H F O S ([M+H] ) 517.0514; found:
17.0498.
8-(3-Methoxyphenyl)naphthalen-1-yl nonafluorobutanesulfonate (4i) (Table 2, entry
9
). Naphthol 3i (71.0 mg, 0.28 mmol) was subjected to the nonaflation with 6.5 equiv of NfF for
6
2
h. After preparative TLC (SiO , hexane/EtOAc = 8/1), 4i (129 mg, 86%) was obtained as a
1
3
yellow solid. Mp. 67.8−69.4 ºC; H NMR (400 MHz, CDCl ): δ 3.84 (3H, s), 6.95-6.99 (3H, m),
7.35 (1H, t, J = 8.0 Hz), 7.46−7.52 (3H, m), 7.59 (1H, t, J = 8.0 Hz ), 7.82 (1H, d, J = 8.0 Hz) ,
1
3
1
3
7.97 (1H, d, J = 4.0 Hz) ppm; C{ H} NMR (100 MHz, CDCl ): δ 55.3, 113.0, 115.6, 119.7,
1
22.3, 124.5, 125.0, 126.5, 128.1, 128.8, 129.6, 131.9, 136.2, 137.2, 142.9, 145.9, 159.2 ppm
(The perfluorobutyl carbons were not observed.); IR (ATR): 573, 586, 698, 727, 766, 1140, 1192,
−1
+
1
14 9 4
422 cm ; HRMS (ESI-TOF): m/z calcd for C21H F O S ([M+H] ) 533.0464; found: 533.0495.
8-(3-(Trifluoromethyl)phenyl)naphthalen-1-yl nonafluorobutanesulfonate (4j) (Table
2, entry 10). Naphthol 3j (236 mg, 0.82 mmol) was subjected to the nonaflation with 2.0 equiv of
2
NfF for 6 h. After preparative TLC (SiO , hexane/EtOAc = 10/1), 4j (433 mg, 93%) was obtained
1
as a colorless oil. H NMR (400 MHz, CDCl
3
): δ 7.49−7.65 (6H, m), 7.71 (2H, s), 8.00 (2H, t, J
1
3
1
3
=
8.0 Hz) ppm; C{ H} NMR (100 MHz, CDCl
3
): δ 120.0, 124.2 (q, JCF = 3.3 Hz), 124.27 (q,
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2
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
J
CF = 270.8 Hz), 124.29, 125.4, 126.5, 128.4, 128.7, 129.7, 130.3 (q, JCF = 32.1 Hz), 132.2,
32.8, 135.7, 136.3, 142.5, 145.5 ppm (One aromatic carbon signal is overlapped. The
perfluorobutyl carbons were not observed.); IR (ATR): 586, 762, 827, 1009, 1125, 1198, 1331
1
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
−1
＋·
10 12 3
cm ; HRMS (DART-TOF): m/z calcd for C21H F O S (M ) 570.0154; found: 570.0144.
8
-(3-Isopropylphenyl)naphthalen-1-yl nonafluorobutanesulfonate (4k) (Table 2, entry
1
1). Naphthol 3k (57.0 mg, 0.22 mmol) was subjected to the nonaflation with 2.0 equiv of NfF
2
for 8 h. After preparative TLC (SiO , hexane/EtOAc = 10/1), 4k (106 mg, 89%) was obtained as
1
a yellow oil. H NMR (400 MHz, CDCl
3
): δ 1.30 (3H, d, J = 1.3 Hz), 1.32 (3H, d, J = 2.4 Hz),
2.95 (1H, spt, J = 6.8 Hz), 7.23 (1H, dd, J = 1.6, 1.8 Hz), 7.27 (2H, dd, J = 1.6, 7.0 Hz), 7.37 (1H,
d, J = 8.0 Hz), 7.40−7.55 (3H, m), 7.58 (1H, t, J = 7.6, 7.8 Hz) , 7.89 (1H, dd, J = 1.6, 8.4 Hz),
1
3
1
7
1
1
1
5
3
.94 (1H, dd, J = 1.2, 8.0 Hz) ppm; C{ H} NMR (100 MHz, CDCl ): δ 23.8, 24.0, 34.2, 119.7,
24.6, 124.9, 125.5, 126.5, 127.1, 127.7, 127.8, 128.0, 129.6, 132.0, 136.3, 137.8, 141.5, 146.1,
48.3 ppm (The perfluorobutyl carbons were not observed.); IR (ATR): 584, 764, 826, 1009,
−1
+
18 9 3
142, 1196, 1227, 2963 cm ; HRMS (DART-TOF): m/z calcd for C23H F O S ([M+H] )
45.0827; found: 545.0810.
8
-(3-(N,N-Dimethylamino)phenyl)naphthalen-1-yl nonafluorobutanesulfonate (4l)
(
Table 2, entry 12). Naphthol 3l (83.4 mg, 0.32 mmol) was subjected to the nonaflation with 3.0
equiv of NfF for 13 h. After preparative TLC (SiO
27
2
, hexane/EtOAc = 4/1), 4l (167 mg, 97%) was
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6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
3
obtained as a yellow oil. H NMR (400 MHz, CDCl ): δ 2.95 (6H, s), 6.75 (1H, d, J = 8.0 Hz),
6
4
1
1
1
5
.80 (2H, dd, J = 8.0, 1.2 Hz), 7.28 (1H, t, J = 8.0 Hz), 7.43−7.58 (4H, m), 7.88 (1H, dd, J = 8.0,
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
13
1
3
.0 Hz), 7.93 (1H, dd, J = 8.0, 4.0 Hz) ppm; C{ H} NMR (100 MHz, CDCl ): δ 40.8, 112.1,
14.7, 118.7, 119.5, 124.7, 124.8, 126.5, 127.7, 128.4, 129.5, 131.8, 136.3, 138.3, 142.4, 146.1,
50.5 ppm (The perfluorobutyl carbons were not observed.); IR (ATR): 571, 584, 698, 826, 1011,
−
1
+
17 9 3
142, 1196 cm ; HRMS (DART-TOF): m/z calcd for C22H F NO S ([M+H] ) 546.0780; found:
46.0784.
[1,2’-Binaphthalen]-8-yl nonafluorobutanesulfonate (4m) (Table 2, entry 13). Naphthol
3m (37.0 mg, 0.14 mmol) was subjected to the nonaflation with 3.0 equiv of NfF for 4 h. After
preparative TLC (SiO
2
, hexane/EtOAc = 4/1), 4m (61.5 mg, 81%) was obtained as a pale yellow
1
solid. Mp. 120.1−121.4 ºC; H NMR (400 MHz, CDCl
3
): δ 7.43−7.54 (5H, m), 7.56 (1H, dd, J =
7
.0, 1.2 Hz), 7.61 (1H, t, J = 8.0 Hz), 7.86−7.90 (4H, m), 7.93 (1H, dd, J = 8.2, 1.2 Hz), 7.97 (1H,
13
1
3
dd, J = 8.0, 1.2 Hz) ppm; C{ H} NMR (100 MHz, CDCl ): δ 119.8, 124.7, 125.1, 125.9, 126.1,
1
1
1
26.6, 127.2, 127.6, 127.1, 128.0, 128.1, 128.4, 129.6, 132.4, 132.7, 133.3, 136.3, 137.4, 139.2,
45.9 ppm (The perfluorobutyl carbons were not observed.); IR (ATR): 584, 725, 746, 764, 822,
−
1
−
12 9 3
138, 1188, 1429 cm ; HRMS (ESI-TOF): m/z calcd for C24H F O S ([M−H] ) 551.0369;
found: 551.0343.
General procedure for intramolecular C−H arylation. A suspension of an
28
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Page 29 of 40
The Journal of Organic Chemistry
1
2
3
4
2 3 3 4
8-aryl-1-naphthyl nonaflate, Pd (dba) (5 mol %), SPhos (12 mol %), K PO (4.0 equiv), and
5
6
7
8
9
1
1
1
1
1
1
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5
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5
5
5
5
6
1
-AdCO
2
H (2.0 equiv) in DMA (4.0 mL/1 mmol 8-aryl-1-naphthyl nonaflate) was heated at
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
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8
9
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0
1
10 °C for 24 h. After cooling to rt, 1 M aq. HCl was added. The mixture was extracted with
EtOAc three times, and the combined organic phases were washed with water and brine, dried
2 4
over Na SO , and concentrated under vacuum. Purification by chromatography gave the desired
product.
Fluoranthene (5a) (Table 3, entry 2). Nonaflate 4a (50.2 mg, 0.10 mmol) was subjected
1
5
2
to the intramolecular C−H arylation. After preparative TLC (SiO , hexane/EtOAc = 10/1), 5a
1
(19.9 mg, 98%) was obtained as a white solid. H NMR (400 MHz, CDCl
3
): δ 7.37 (2H, dd, J
1
3
1
=5.2, 2.8 Hz), 7.62 (2H, t, J =8.4 Hz), 7.83 (2H, d, J =8.4 Hz), 7.89−7.94 (4H, m) ppm; C{ H}
3
NMR (100 MHz, CDCl ): 120.0, 121.5, 126.6, 127.5, 127.9, 130.0, 132.4, 136.9, 139.4 ppm.
4
9
8-Methylfluoranthene (5b) (Table 3, entry 3 and Table 4, entry 5). Nonaflate 4h (103
mg, 0.20 mmol) was subjected to the intramolecular C−H arylation. After preparative TLC three
times (SiO
2
, hexane/EtOAc = 10/1, three times), methylfluoranthenes (39.3 mg, 91%) were
1
obtained as an orange solid. The ratio of 5b to 6a was determined by H NMR to be 50:1.
Alternatively, nonaflate 4f (58.0 mg, 0.11 mmol) was subjected to the intramolecular C−H
2
arylation. After preparative TLC (SiO , hexane/EtOAc = 10/1), 5b (20.5 mg, 84%) was obtained
4
9 1
3
as a yellow solid. 5b: H NMR (400 MHz, CDCl ): δ 2.49 (3H, s), 7.18 (1H, dd, J = 8.0, 8.4
29
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