Practical one-pot preparation of ketones from aryl and alkyl bromides with aldehydes and DIH via Grignard reagents

Article abstract of DOI:10.1016/j.tet.2012.05.059

Various diaryl ketones, alkyl aryl ketones, and dialkyl ketones were efficiently prepared in good yields by the reactions of the Grignard reagents derived from aryl or alkyl bromides, followed by the reactions with aromatic or aliphatic aldehydes and the subsequent treatment with 1,3-diiodo-5,5- dimethylhydantoin and K₂CO₃, in a one-pot method. The same treatment of aromatic bromides bearing electron-withdrawing groups, such as ester, nitrile, ketone, and nitro groups with i-PrMgCl·LiCl or PhMgCl instead of Mg, also provided the corresponding diaryl and alkyl aryl ketones in good yields. The above methods are simple and practical transition-metal-free methods for the preparation of various diaryl ketones and alkyl aryl ketones bearing electron-rich aromatic groups and electron-deficient aromatic groups, as well as dialkyl ketones.

Full text of DOI:10.1016/j.tet.2012.05.059

Tetrahedron 68 (2012) 6557e6564
Contents lists available at SciVerse ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Practical one-pot preparation of ketones from aryl and alkyl bromides with
aldehydes and DIH via Grignard reagents
*
Souya Dohi, Katsuhiko Moriyama, Hideo Togo
Graduate School of Science, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 24 April 2012
Received in revised form 14 May 2012
Accepted 15 May 2012
Available online 29 May 2012
Various diaryl ketones, alkyl aryl ketones, and dialkyl ketones were efficiently prepared in good yields
by the reactions of the Grignard reagents derived from aryl or alkyl bromides, followed by the
reactions with aromatic or aliphatic aldehydes and the subsequent treatment with 1,3-diiodo-
5,5-dimethylhydantoin and K2CO3, in a one-pot method. The same treatment of aromatic bromides
bearing electron-withdrawing groups, such as ester, nitrile, ketone, and nitro groups with i-PrMgCl$LiCl
or PhMgCl instead of Mg, also provided the corresponding diaryl and alkyl aryl ketones in good yields.
The above methods are simple and practical transition-metal-free methods for the preparation of various
diaryl ketones and alkyl aryl ketones bearing electron-rich aromatic groups and electron-deficient
aromatic groups, as well as dialkyl ketones.
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction
prepared from aromatic and aliphatic halides with Mg13 and the
practical scale-up preparation with them is easy. Today, as typical
Aromatic and aliphatic ketones are very important and useful
building blocks and structural elements for the preparation of
pharmaceuticals, agrochemicals, and functional materials.1 Gener-
ally, aromatic and aliphatic ketones are prepared by the oxidation
of secondary alcohols.2 In addition, aromatic ketones, such as diaryl
ketones and alkyl aryl ketones, are prepared by the FriedeleCrafts
reaction of arenes and acyl halides with Lewis acids,3,4 the Hou-
beneHoesch reaction of arenes and nitriles with Lewis acid,4,5 the
Fries rearrangement of aryl esters with Lewis acids,4,6 the reaction
of RCu(CN)M (M¼ZnX, MgX, Li) with acyl halides,7 the reaction of
ArZnBr and acyl halides or carboxylic anhydrides with CoBr2,8 the
and practical transition-metal-free methods for the preparation of
ketones with the Grignard reagents and carboxylic acid derivatives,
the reaction of RMgX with nitriles14 and the reaction of RMgX with
Weinreb amides15 are well known. Moreover, recently, it was
reported that aromatic and aliphatic ketones were prepared by the
reaction of RMgX with acyl halides in the presence of N-methyl-
pyrrolidine under transition-metal-free conditions.16 Although
moisture-sensitive acyl halides were used, we are very much in-
terested in this report. Obviously, the synthetic use of aldehydes
and RMgX for the preparation of ketones via oxidative reaction is
very attractive, as many kinds of aldehydes are easily available. The
oxidative reaction of aldehydes with organovanadiums prepared
from RMgX and VCl3 was reported in the past.17 However, there are
still some drawbacks, such as the low yields of ketones depending
on the substrates and the use of a transition metal. In order to re-
alize a practical, less toxic, less expensive, and therefore environ-
mentally benign organic synthesis, the emergence of new methods
for the preparation of aromatic and aliphatic ketones, such as diaryl
ketones, alkyl aryl ketones, and dialkyl ketones, from easily avail-
able substrates, i.e., aromatic and aliphatic bromides with alde-
hydes, without any transition metals under mild conditions is
greatly demanded. On the other hand, the synthetic use of molec-
ular iodine and iodine-related reagents, such as 1,3-diiodo-5,5-
dimethylhydantoin (DIH), in organic synthesis has become very
popular, because they are highly affordable and have very low
toxicity.18 Recently, we reported the preparation of aromatic ke-
tones by the reaction of aromatic bromides with n-BuLi, followed
decarboxylative coupling reaction of a-oxocarboxylates and ArBr
with CuBr and Pd(F6-acac)2,9 the Ni-catalyzed (NiCl2(DME)/dppp/
Zn) coupling reaction of aryl iodides to nitriles,10 and the
direct oxidative reaction of alkylarenes with oxidants, such as
N-hydroxyphthalimide, o-iodylbenzoic acid (IBX), and H2O2 with
HBr.11 Recently, the acylation of organometallic reagents, such as
organomanganese, organozinc, organocopper, organoiron, and
others, has been actively studied.12 However, a less-toxic and
transition-metal-free preparation of aromatic and aliphatic ketones
from easily available compounds is still greatly required in view of
environmentally benign organic synthesis. In this regard, the syn-
thetic use of the Grignard reagents for the preparation of ketones is
very attractive because the Grignard reagents can be easily
* Corresponding author. Tel./fax: þ81 43 290 2792; e-mail address: togo@faculty.
chiba-u.jp (H. Togo).
0040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2012.05.059

6558
S. Dohi et al. / Tetrahedron 68 (2012) 6557e6564
Table 1
by the reaction with aldehydes and the subsequent oxidation with
molecular iodine in the presence of K2CO3.19 We believe this is
a simple and useful method for the preparation of aromatic ketones
in good yields. However, only aromatic bromides and iodides can be
used in this reaction. Therefore, dialkyl ketones cannot be prepared.
Moreover, aromatic bromides bearing electron-withdrawing
groups, such as ester, nitrile, and nitro groups, cannot be used as
the substrate. As part of our ongoing studies on the use of molecular
iodine and iodine-related reagents for organic synthesis,20 we
would like to report a simple and practical method for the prepa-
ration of various ketones from the reactions of aryl or alkyl bro-
mides with Mg, i-PrMgX,21 or PhMgCl,22 followed by the reaction
with aldehydes and the subsequent oxidation with DIH and K2CO3.
One-pot preparation of aromatic ketones from aryl bromides and aldehydes with
DIH via Grignard reagents (1)
Entry
X
RCHO
Time (h)
Yield (%)
1
2
3
4
CH3
CH3(CH2)6CHO
CH3(CH2)6CHO
c-C6H11CHO
20
20
20
20
67
47a
87
2. Results and discussion
(CH3)3CCHO
80
First, treatment of Grignard reagents, such as p-tolylmagnesium
bromide and n-octylmagnesium bromide, with ethyl octanoate
generated mainly tertiary alcohols and the starting esters, together
with trace amounts of heptyl p-tolyl ketone and heptyl octyl ketone,
respectively, as shown in Scheme 1. Even if the amounts of the
Grignard reagents were reduced or the reaction temperature was
lowered, the esters could not be obtained as the main product due to
the rapid decomposition of the first addition products to ketones,
and subsequent rapid addition of the Grignard reagents to the
formed ketones. Therefore, we planned the addition reaction of the
Grignard reagents to aldehydes and the subsequent oxidation to
ketones in a one-pot procedure, in hopes of obtaining the ketones in
good yield. Thus, p-bromotoluene (1.3 equiv) was treated with Mg
(1.5 equiv) to generate p-tolylmagnesium bromide. After 1 h, octanal
(5 mmol) was added at 0 ꢀC and the mixture was stirred for 2 h at
room temperature. Then, DIH (0.8 equiv), K2CO3 (2.1 equiv), and t-
BuOH were added and the obtained mixture was refluxed for 20 h to
provide heptyl p-tolyl ketone in 67% yield, as shown inTable 1 (entry
1). When other aldehydes, such as cyclohexanecarboxaldehyde
bearing a secondary alkyl group, pivalaldehyde bearing a tertiary
alkyl group, p-substituted aromatic aldehydes bearing Me,
5
6
7
8
9
10
11
FG¼Me
FG¼Me
FG¼Me
FG¼MeO
FG¼F
19
19
19
19
15
20
15
76
61a
89b
79
74
81
FG¼Cl
FG¼CF3
80
12
20
81
13
20
76
14
15
16
Cl
CH3(CH2)6CHO
c-C6H11CHO
(CH3)3CCHO
20
20
20
69
73
81
17
18
19
20
21
FG¼Me
FG¼MeO
FG¼F
20
20
20
20
22
93
86
82
65
77
FG¼Cl
FG¼CF3
22
20
73
23
20
84
24
25
26
CF3
CH3(CH2)6CHO
c-C6H11CHO
(CH3)3CCHO
20
20
20
66
74
68
27
28
29
30
31
FG¼Me
FG¼MeO
FG¼F
23
23
20
20
20
73
80
82
76
72
FG¼Cl
FG¼CF3
Scheme 1. Reaction of Grignard reagents and ethyl octanoate.

S. Dohi et al. / Tetrahedron 68 (2012) 6557e6564
6559
Table 1 (continued )
Table 2
One-pot preparation of aromatic and aliphatic ketones from alkyl bromides and
aldehydes with DIH via Grignard reagents (2)
Entry
X
RCHO
Time (h)
23
Yield (%)
89
32
33
20
85
a
I2 (2.0 equiv) instead of DIH was used.
Reaction was carried out with 20 mmol of p-tolualdehyde.
b
Entry
R0
RCHO
Time (h)
Yield (%)
1
2
3
4
CH3(CH2)7
CH3(CH2)6CHO
CH3(CH2)6CHO
c-C6H11CHO
20
20
20
20
71
37a
74
(CH3)3CCHO
75
MeO, F, Cl, and CF3 groups, 3-pyridinecarboxaldehyde, and 2-
thiophenecarboxaldehyde, were subjected to the same procedure
and conditions, the corresponding aromatic ketones were obtained
in good yields, respectively, (entries 3e5, 8e13). The same treat-
ment of p-bromochlorobenzene and p-bromo(trifluoromethyl)
benzene with Mg, followed by the reaction with octanal, cyclo-
hexanecarboxaldehyde, pivalaldehyde, p-substituted aromatic al-
dehydes bearing Me, MeO, F, Cl, and CF3 groups, 3-
pyridinecarboxaldehyde, and 2-thiophenecarboxaldehyde, gener-
ated the corresponding aromatic ketones in good yields, re-
spectively, (entries 14e33). Thus, using the present method, various
aromatic ketones were obtained in good yields in a one-pot pro-
cedure, starting from aromatic bromides, Mg, aldehydes, and DIH.
When molecular iodine was used instead of DIH, the yields of ke-
tones were decreased due to the weaker oxidizing ability of mo-
lecular iodine (entries 2, 6). This is due tothe stronger iodination and
oxidation ability of DIH than molecular iodine.20k,20m,20n,20u When
the reaction was carried out with 20 mmol of p-tolualdehyde, the
corresponding di(p-tolyl) ketone was obtained in good yield (entry
7). Thus, the present method can be used for the large-scale prep-
aration of aromatic ketones. Octyl bromide (1.5 equiv) was treated
with Mg (1.6 equiv) to form octylmagnesium bromide. After 1 h,
octanal (5 mmol) was added at 0 ꢀC and the mixture was stirred for
2 h at room temperature. Then, DIH (0.8 equiv), K2CO3 (2.1 equiv),
and t-BuOH were added and the obtained mixture was refluxed for
20 h to provide heptyl octyl ketone in 71% yield, as shown in Table 2
(entry 1). Again, DIH was a more efficient oxidant than molecular
iodine (entry 2). When other aldehydes, such as cyclo-
hexanecarboxaldehyde, pivalaldehyde, p-substituted aromatic al-
dehydes bearing Me, MeO, F, Cl, and CF3 groups, 3-
pyridinecarboxaldehyde, and 2-thiophenecarboxaldehyde, were
subjected to the same procedure and conditions, the corresponding
aliphatic and aromatic ketones were obtained in good to moderate
yields, respectively, (entries 3e11). The same treatment of cyclo-
hexyl bromide with Mg, followed by the reaction with octanal,
cyclohexanecarboxaldehyde, pivalaldehyde, and p-substituted aro-
matic aldehydes bearing Me and CF3 groups, provided the corre-
sponding aliphatic and aromatic ketones in good to moderate yields,
respectively, (entries 12e16). Thus, the present reaction can be used
for the preparation of not only aromatic ketones, but also aliphatic
ketones. Then, to extend the synthetic utility of the present reaction,
ethyl p-iodobenzoate and p-bromocyanobenzene were used as ar-
omatic halides bearing ester and cyano groups.
5
6
7
8
9
FG¼Me
FG¼MeO
FG¼F
20
20
21
20
20
86
80
72
67
67
FG¼Cl
FG¼CF3
10
20
53
11
20
75
12
13
14
c-C6H11
CH3(CH2)6CHO
c-C6H11CHO
(CH3)3CCHO
20
20
20
60
60
64
15
16
FG¼Me
FG¼CF3
23
23
76
60
a
I2 (2.0 equiv) instead of DIH was used.
mixtures and the mixtures were stirred for 2 h at room temperature,
respectively. Then, DIH (0.8 equiv), K2CO3 (2.1 equiv), and t-BuOH
were added and the obtained mixtures were refluxed for 20 h to
provide heptyl p-(ethoxycarbonyl)phenyl ketone and p-cyano-
phenyl heptyl ketone in 77% yield and 63% yield, respectively, as
shown in Table 3 (entries 1, 6). When other aldehydes, such as
cyclohexanecarboxaldehyde, pivalaldehyde, and p-substituted ar-
omatic aldehydes bearing Me and CF3 groups, were subjected to the
same procedure and conditions, the corresponding aromatic ke-
tones bearing an ester group and a cyano group were obtained in
good to moderate yields, respectively, (entries 2e5, 7e9). Then, as
a further synthetic application, o-iodonitrobenzene was treated
with PhMgCl (1.3 equiv)22 to generate the corresponding arylmag-
nesium chlorides at ꢁ40 ꢀC for 0.5 h. p-Nitrobenzaldehyde and p-
tolualdehyde (3 mmol) were added to the mixtures and the mix-
tures were stirred for 2 h at room temperature, respectively. As the
next step, DIH (2.4 equiv), K2CO3 (2.1 equiv), and t-BuOH were
added and the obtained mixtures were refluxed to provide o-
nitrophenyl p-nitrophenyl ketone and o-nitrophenyl p-tolyl ketone
in 80% yield and 85% yield, respectively, as shown in Scheme 2. The
same treatment of 4-benzoyl-2-nitro-1-iodobenzene (1.5 mmol)
with PhMgCl (1.1 equiv), followed by the reaction with p-tolualde-
hyde (1.2 equiv) and the subsequent treatment with DIH and K2CO3
Ethyl p-iodobenzoate (1.1 equiv) and p-bromocyanobenzene
(1.3 equiv) were treated with i-PrMgCl$LiCl (1.2e1.3 equiv)21 to
generate the corresponding arylmagnesium chlorides at -15 ꢀC and
0
ꢀC, respectively. Then, octanal (3 mmol) was added to the

6560
S. Dohi et al. / Tetrahedron 68 (2012) 6557e6564
Table 3
One-pot preparation of aromatic ketones from aromatic bromides bearing electron-
withdrawing group and aldehydes and DIH via Grignard reagents (2)
Entry
1
RCHO
Time (h)
20
Yield (%)
77
CH3(CH2)6CHO
2
3
c-C6H11CHO
20
20
79
68
(CH3)3CCHO
4
5
FG¼Me
FG¼CF3
19
20
88
75
Scheme 2. One-pot preparation of aromatic ketones from aromatic iodides bearing
electron-withdrawing group and aldehydes and DIH via Grignard reagents (3).
aliphatic aldehydes, and the subsequent treatment with DIH and
K2CO3 in a one-pot method. The same treatment of aromatic ha-
lides bearing ester, cyano, ketone, and nitro groups with
i-PrMgCl$LiCl or PhMgCl also provided the corresponding aromatic
ketones in good to moderate yields. Thus, various diaryl ketones
and alkyl aryl ketones bearing electron-rich aromatic groups and
electron-deficient aromatic groups, as well as dialkyl ketones, could
be prepared efficiently with the simple and practical experimental
procedure. The reactions can be carried out under transition-metal-
free conditions and used as an environmentally benign method for
the preparation of various aromatic and aliphatic ketones.
6
7
CH3(CH2)6CHO
20
20
63
64
c-C6H11CHO
4. Experimental
4.1. General
8
9
FG¼Me
FG¼CF3
22
20
77
52
1H NMR,13C NMR, and 19F NMR spectra were obtained with JEOL-
JNM-ECX400, JEOL-JNM-ECS400, and JEOL-JNM-ECA500 spectrom-
eters. Chemical shifts are expressed in parts per million downfield
provided 4-benzoyl-2-nitrophenyl p-tolyl ketone in 71% yield. On
the other hand, the same treatment of p-bromocyanobenzene and
o-nitroiodobenzene with n-BuLi, followed by the reaction with al-
dehydes and the subsequent oxidation with molecular iodine in the
presence of K2CO3 did not generate the corresponding ketones,
respectively, (the previous method).19 Thus, the present method
involving the reaction of electron-poor aromatic bromides bearing
ester, nitrile, ketone, and nitro groups, with i-PrMgX or PhMgCl,
followed by the reaction with aldehydes and the subsequent oxi-
dation with DIH, can be used for the preparation of diaryl ketones
and alkyl aryl ketones bearing electron-deficient aromatic groups.
from TMS in
d units. Mass spectra were recorded on JMS-T100GCV,
JMS-HX110, and Thermo LTQ Orbitrap spectrometers. IR spectra
were measured with a JASCO FT/IR-4100 spectrometer. Melting
points were determined with a Yamato Melting Point Apparatus
Model MP-21. Silica gel 60 (Kanto Kagaku Co.) was used for column
chromatography and Wakogel B-5F was used for preparative TLC.
4.1.1. Typical experimental procedure for one-pot conversion of bro-
mides into ketones (1). [Using Mg turnings]: A solution of p-bro-
motoluene (1112 mg, 6.5 mmol) in dry THF (4 mL) was added
dropwise to Mg turnings (182 mg 7.5 mmol) in THF (6 mL) at room
temperature and then, the mixture was stirred at room tempera-
3. Conclusion
ture for
1 h. A solution of p-chlorobenzaldehyde (703 mg,
Various aromatic and aliphatic ketones bearing electron-
donating groups and electron-withdrawing groups, including the
pyridyl group and the thienyl group, were efficiently prepared by
the reactions of aryl bromides and alkyl bromides with Mg, re-
spectively, followed by the reactions with aromatic aldehydes or
5.0 mmol) in THF (5 mL) was added to the mixture at 0 ꢀC and the
obtained mixture was stirred at room temperature for 2 h. Then,
DIH (1520 mg, 4.0 mmol), K2CO3 (1451 mg, 10.5 mmol), and t-BuOH
(15 mL) were added and the obtained mixture was stirred for 20 h
at refluxing conditions. The reaction mixture was quenched with

S. Dohi et al. / Tetrahedron 68 (2012) 6557e6564
6561
satd aq Na2SO3 (10 mL) and was extracted with CHCl3 (3ꢂ25 mL).
The organic layer was washed with brine and dried over Na2SO4.
Purification by short column chromatography (silica gel; hexane/
CHCl3¼1:1) yielded p-chlorophenyl p-tolyl ketone (934 mg, 81%).
J¼8.2 Hz, 2H), 7.81 (d, J¼9.1 Hz, 2H); 13C NMR (100 MHz, CDCl3)
d¼21.6, 55.4, 113.4, 128.8, 130.0, 130.4, 132.4, 135.5, 142.6, 163.0,
195.3.
4.1.9. pꢀ-Fluorophenyl p-tolyl ketone. Mp 97e98 ꢀC lit.26 mp
96e97 C; IR (Nujol) 1647 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d
¼2.44
€
4.1.2. Typical experimental procedure for one-pot conversion of
bromides into ketones (2). [Using i-PrMgCl$LiCl via Br-Exchange]: A
solution of p-bromobenzonitrile (710 mg, 3.9 mmol) in dry THF
(2 mL) was added dropwise to i-PrMgCl$LiCl (3.9 mL, ca. 1 M in
THF, 3.9 mmol) at 0 ꢀC and then, the mixture was stirred at 0 ꢀC for
3 h. Then, a solution of p-tolualdehyde (360 mg, 3.0 mmol) in THF
(3 mL) was added to the mixture at ꢁ10 ꢀC and the obtained
mixture was stirred at ꢁ10 ꢀC for 2 h, and then, at 0 ꢀC for 1 h. DIH
(912 mg, 2.4 mmol), K2CO3 (871 mg, 6.3 mmol), and t-BuOH (9 mL)
were added to the mixture and the obtained mixture was stirred
for 20 h at refluxing conditions. The reaction mixture was
quenched with satd aq Na2SO3 (10 mL) and was extracted with
CHCl3 (3ꢂ20 mL). The organic layer was washed with brine and
dried over Na2SO4. Purification by short column chromatography
(silica gel; CHCl3) yielded p-cyanophenyl p-tolyl ketone (511 mg,
77%).
(s, 3H), 7.11e7.17 (m, 2H), 7.28 (d, J¼7.9 Hz, 2H), 7.68 (d, J¼8.2 Hz,
2H), 7.79e7.84 (m, 2H); 13C NMR (100 MHz, CDCl3)
d¼21.6, 115.3 (d,
JCeF¼21.1 Hz), 129.0, 130.0, 132.4 (d, JCeF¼8.6 Hz), 134.1 (d,
JCeF¼2.9 Hz), 134.7, 143.2, 165.2 (d, JCeF¼254.8 Hz), 195.0; 19F NMR
(471 MHZ, CDCL3)
d¼106.3.
4.1.10. p-Chlorophenyl p-tolyl ketoꢁn1e. Mp 128e129 ꢀC (lit.27 mp
ꢀ
€
126e127 C); IR (Nujol) 1644 cm
;
1H NMR (400 MHz, CDCl3)
d
¼2.44 (s, 3H), 7.28 (d, J¼7.7 Hz, 2H), 7.45 (d, J¼8.1 Hz, 2H), 7.69 (d,
J¼8.2 Hz, 2H), 7.75 (d, J¼8.8 Hz, 2H); 13C NMR (100 MHz, CDCl3)
d¼21.6, 128.5, 129.1, 130.1, 131.3, 134.5, 136.2, 138.6, 143.5, 195.2.
4.1.11. p-Tolyl p-trifluoromethylphenyl ketone. Mp 144e145 ꢀC (lit.28
ꢁ1
;
1H NMR (500 MHz, CDCl3)
ꢀ
€
mp. 136e137 C); IR (nujol) 1647 cm
¼2.46 (s, 3H), 7.31 (d, J¼8.0 Hz, 2H), 7.70e7.77(m,4H),7.87(d,J¼8.0 Hz,
2H); 13C NMR (125 MHz, CDCl3)
¼21.7, 123.7 (q, JCeF¼272.3 Hz), 125.3
(q, JCeF¼3.6 Hz), 129.2, 130.0, 130.3, 133.4 (q, JCeF¼32.4 Hz), 134.0, 141.1,
144.1, 195.2; 19F NMR (471 MHz, CDCl3)
¼ꢁ62.9.
d
d
4.1.3. Typical experimental procedure for one-pot conversion of
bromides into ketones (3). [Using PhMgCl via I-exchange]: A so-
lution of o-nitroiodobenzene (896 mg, 3.6 mmol) in dry THF
(2 mL) was added dropwise to PhMgCl (2.0 mL, ca. 2 M in THF,
3.9 mmol) at ꢁ40 ꢀC and the obtained mixture was stirred at
ꢁ40 ꢀC for 0.5 h. Then, a solution of p-tolualdehyde (360 mg,
3.0 mmol) in THF (3 mL) was added to the mixture at ꢁ40 ꢀC and
the obtained mixture was stirred at ꢁ40 ꢀC for 2 h and then, at
0 ꢀC for 1 h. DIH (2736 mg, 7.0 mmol), K2CO3 (871 mg, 6.3 mmol),
and t-BuOH (9 mL) were added and the obtained mixture was
stirred for 20 h at refluxing conditions. The reaction mixture was
quenched with satd aq Na2SO3 (10 mL) and was extracted with
CHCl3 (3ꢂ20 mL). The organic layer was washed with brine and
dried over Na2SO4. Purification by short column chromatography
(silica gel; hexane/CHCl3¼1:1) yielded o-nitrophenyl p-tolyl ke-
tone (615 mg, 85%).
d
4.1.12. 3-Pyridyl p-tolyl ketone. Mp 76e78 ꢀC (lit.29 mp 76e77 ꢀC);
ꢁ1
€
IR (Nujol) 1650 cm
;
1H NMR (400 MHz, CDCl3)
d
¼2.46 (s, 3H),
7.32 (d, J¼7.9 Hz, 2H), 7.45 (ddd, J¼7.9, 4.9, 0.9 Hz, 1H), 7.74 (d,
J¼8.4 Hz, 2H), 8.10 (dt, J¼7.9, 2.0 HZ, 1H), 8.80 (dd, J¼4.9, 2.0 Hz,
1H), 8.98 (dd, J¼2.0, 0.9 Hz, 1H); 13C NMR (100 MHz, CDCl3):
¼21.7,
d
123.3, 129.3, 130.2, 133.5, 134.1, 137.1, 144.2, 150.8, 152.6, 194.5.
4.1.13. 2-Thienyl p-tolyl ketone. Mp 74e75 ꢀC (lit.30 mp
ꢁ1
ꢀ
€
75.0e75.6 C); IR (Nujol) 1627 cm
¼2.44 (s, 3H), 7.14e7.17 (m, 1H), 7.30 (d, J¼7.9 Hz, 2H), 7.64 (dd,
;
1H NMR (400 MHz, CDCl3)
d
J¼5.0, 1.1 Hz, 2H), 7.70 (dd, J¼6.1, 1.1 Hz, 1H), 7.79 (d, J¼8.2 Hz, 2H);
13C NMR (100 MHz, CDCl3)
135.4, 143.0, 143.8, 187.9.
d
¼21.6, 127.8, 129.1, 129.4, 133.8, 134.4,
4.1.4. Heptyl p-tolyl ketone. Mp 34 ꢀC (lit.23 colorless solid); IR
4.1.14. p-Chlorophenyl heptyl ketone. Mp 59e60 C; IR (nujol)
1694 cmꢁ1 1H NMR (400 MHz, CDCl3)
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€
ꢁ1
(nujol) 1690 cm
;
1H NMR (500 MHz, CDCl3)
d
¼0.88 (t, J¼7.2 Hz,
;
d
¼0.88 (t, J¼7.0 Hz, 3H),
€
3H), 1.24e1.40 (m, 8H), 1.72 (quint, J¼7.2 Hz, 2H), 2.41 (s, 3H), 2.93
1.25e1.41 (m, 8H),1.72 (quint, J¼7.5 Hz, 2H), 2.93 (t, J¼7.5 Hz, 2H), 7.42
(t, J¼7.2 Hz, 2H), 7.25 (d, J¼8.3 Hz, 2H), 7.86 (d, J¼8.3 Hz, 2H); 13C
(d, J¼8.8 Hz, 2H), 7.90 (d, J¼8.8 Hz, 2H); 13C NMR (100 MHz, CDCl3)
NMR (125 MHz, CDCl3)
d
¼14.1, 21.6, 22.6, 24.5, 29.1, 29.4, 31.7, 38.5,
d
¼14.0, 22.6, 24.2, 29.1, 29.2, 31.7, 38.6,128.8,129.4,135.3,139.2,199.2;
128.2, 129.2, 134.6, 143.5, 200.3.
HRMS (APCI) Calcd for C14H20OCl [MþH]þ 239.1197, Found 239.1195.
4.1.5. Cyclohexyl p-tolyl ketone. Mp 65e68 ꢀC (lit.24 mp 61e63 ꢀC);
4.1.15. p-Chlorophenyl cyclohexyl ketone. Mp 61e62 ꢀC (lit.31 mp
ꢁ1
ꢁ1
IR (Nujol) 1685 cm
;
1H NMR (400 MHz, CDCl3)
d
¼1.19e1.31 (m,
59e60 C); IR (Nujol) 1687 cm
¼1.21e1.32 (m, 1H), 1.32e1.55 (m, 4H), 1.70e1.78 (m, 1H),
;
1H NMR (400 MHz, CDCl3)
ꢀ
€
€
1H), 1.32e1.50 (m, 4H), 1.70e1.78 (m, 1H), 1.79e1,94 (m, 4H), 2.39
(s, 3H), 3.19e3.28 (m, 1H), 7.24 (d, J¼7.9 Hz, 2H), 7.84 (d, J¼8.2 Hz,
d
1.81e1.90 (m, 4H), 3.16e3.24 (m, 1H), 7.43 (d, J¼8.6 Hz, 2H), 7.88 (d,
2H); 13C NMR (100 MHz, CDCl3)
129.1, 133.7, 143.3, 203.4.
d¼21.5, 25.8, 25.9, 29.4, 43.4, 128.3,
J¼8.6 Hz, 2H); 13C NMR (125 MHz, CDCl3)
¼25.8, 25.9, 29.3, 45.6,
d
128.9, 129.7, 134.6, 139.1, 202.6.
4.1.6. t-Butyl p-tolyl ketone. Colorless oil (lit.25 oil); IR (neat)
4.1.16. t-Butyl p-chlorophenyl ketone. Colorless oil (lit.32 oil); IR
1672 cmꢁ1
;
1H NMR (400 MHz, CDCl3)
d
¼1.35 (s, 9H), 2.37 (s, 3H),
(neat) 1676 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d
¼1.34 (s, 9H), 7.38 (d,
7.19 (d, J¼7.9 Hz, 2H), 7.66 (d, J¼8.4 Hz, 2H); 13C NMR (100 MHz,
J¼8.4 Hz, 2H), 7.67 (d, J¼8.4 Hz, 2H); 13C NMR (100 MHz, CDCl3)
CDCl3)
d
¼21.3, 28.1, 44.0, 128.3, 128.6, 135.3, 141.4, 208.2.
d¼28.0, 44.2, 128.3, 129.5, 136.5, 137.2, 207.6.
4.1.7. Di(p-tolyl) ketꢁon1 e. Mp 92e93 ꢀC (commercial, mp 90e93 ꢀC);
4.1.17. p-Anisyl p-chlorophenyl ketone. Mp 122e123 ꢀC (lit.33 mp
ꢁ1
;
1H NMR (500 MHz, CDCl3)
IR (Nujol) 1645 cm
;
1H NMR (400 MHz, CDCl3)
d¼2.44 (s, 6H),
119e120 C); IR (Nujol) 1638 cm
ꢀ
€
€
7.27 (d, J¼8.4 Hz, 4H), 7.70 (d, J¼8.4 Hz, 4H); 13C NMR (100 MHz,
d
¼3.89 (s, 3H), 6.97 (d, J¼8.9 Hz, 2H), 7.45 (d, J¼8.6 Hz, 2H), 7.71 (d,
CDCl3)
d
¼21.6, 128.9, 130.2, 135.2, 142.9, 196.3.
J¼8.6 Hz, 2H), 7.80 (d, J¼8.9 Hz, 2H); 13C NMR (125 MHz, CDCl3)
d¼55.5, 113.7, 128.5, 129.8, 131.1, 132.4, 136.5, 138.3, 163.4, 194.2.
4.1.8. p-Anisyl p-tolyl ketone. Mp 89e90 ꢀC (lit.26 mp 88e89 ꢀC); IR
(Nujol) 1644 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d
¼2.43 (s, 3H), 3.88
4.1.18. p-Chlorophenyl p-fluorophenyl ketone. Mp 116e118 ꢀC (lit.34
€
mp 118e119 ꢀC); IR (Nujol) 1649 cmꢁ1; 1H NMR (400 MHz, CDCl3)
€
(s, 3H), 6.96 (d, J¼9.1 Hz, 2H), 7.27 (d, J¼7.7 Hz, 2H), 7.68 (d,

6562
S. Dohi et al. / Tetrahedron 68 (2012) 6557e6564
d
¼7.17 (t, J¼8.6 Hz, 2H), 7.46 (d, J¼8.4 Hz, 2H), 7.72 (d, J¼8.4 Hz, 2H),
7.83e7.88 (m, 4H); 13C NMR (125 MHz, CDCl3)
d
¼115.8 (d, JCeF¼22.8 Hz),
7.78e7.84 (m, 2H); 13C NMR (100 MHz, CDCl3)
d¼115.6 (d,
123.6 (q, JCeF¼272.3 Hz), 125.4 (q, JCeF¼3.6 Hz), 129.9, 132.8 (d,
JCeF¼22.1 Hz), 128.6, 131.2, 132.5 (d, JCeF¼8.6 Hz), 133.4 (d,
JCeF¼9.6 Hz), 133.0 (d, JCeF¼3.6 Hz), 133.8 (q, JCeF¼33.6 Hz), 140.6, 165.7
JCeF¼2.9 Hz), 135.7, 138.9, 165.4 (d, JCeF¼253.2 Hz), 193.9; 19F NMR
(d, JCeF¼255.5 Hz), 194.0; 19F NMR (471 MHz, CDCl3)
¼ꢁ104.4, ꢁ62.9.
d
(471 MHz, CDCl3)
d¼ꢁ105.3.
4.1.28. Di(p-trifluoromethylphenyl) ketone. Mp 108e110 ꢀC (lit.41
4.1.19. Di(p-chlorophenyl) ketone. Mp 144 ꢀC (commercial, mp.
mp. 107e108 C); IR (nujol) 1655 cmꢁ1; 1H NMR (500 MHz, CDCl3)
ꢀ
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ꢁ1
144e146 C); IR (nujol) 1654 cm
;
1H NMR (500 MHz, CDCl3)
d
¼7.79 (d, J¼8.0 Hz, 4H), 7.91 (d, J¼8.0 Hz, 4H); 13C NMR (125 MHz,
ꢀ
€
d
¼7.47 (d, J¼8.6 Hz, 4H), 7.72 (d, J¼8.6 Hz, 4H); 13C NMR (125 MHz,
CDCl3)
d
¼123.5 (q, JCeF¼272.6 Hz),125.6 (q, JCeF¼3.9 Hz),130.2,134.3
CDCl3)
d
¼128.7, 131.3, 135.5, 139.1, 194.2.
(q, JCeF¼32.7 Hz), 139.7, 194.4; 19F NMR (471 MHz, CDCl3)
¼ꢁ63.0.
d
4.1.20. p-Chlorophenyl
p-trifluoromethylphenyl
ketone. Mp
;
4.1.29. 3-Pyridyl p-trifluoromethylphenyl ketone. Mp 53e54 ꢀC; IR
35
ꢁ1
120e122 ꢀC (lit. colorless solid); IR (nujol) 1649 cm
1H NMR
(nujol) 1654 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d
¼7.49 (ddd, J¼7.9, 4.9,
€
€
(500 MHz, CDCl3)
d
¼7.49 (d, J¼8.6 Hz, 2H), 7.74e7.78 (m, 4H), 7.87 (d,
0.8 Hz, 1H), 7.80 (d, J¼8.6 Hz, 2H), 7.93 (d, J¼8.6 Hz, 2H), 8.14 (ddd,
J¼8.1 Hz, 2H); 13C NMR (125 MHz, CDCl3)
¼123.6 (q, JCeF¼272.3 Hz),
d
J¼7.9, 2.2, 1.8 Hz, 1H), 8.86 (dd, J¼4.9, 1.8 Hz, 1H), 9.00 (dd, J¼2.2,
125.5 (q, JCeF¼3.6 Hz), 128.9, 130.0, 131.5, 133.9 (q, JCeF¼32.4 Hz),
0.8 Hz, 1H); 13C NMR (100 MHz, CDCl3)
d
¼123.48 (q, JCeF¼272.9 Hz),
135.0, 139.7, 140.3, 194.3; 19F NMR (471 MHz, CDCl3)
d
¼ꢁ62.9.
123.54, 125.7 (q, JCeF¼3.7 Hz), 130.1, 132.3, 134.4 (q, JCeF¼32.8 Hz),
137.2, 139.6, 151.0, 153.4, 193.8; 19F NMR (471 MHz, CDCl3)
d¼63.0;
4.1.21. p-Chlorophenyl 3-pyridyl ketone. Mp 87e89 ꢀC (lit.36 mp.
HRMS (APCI) Calcd for C13H9ONF3 [MþH]þ 252.0631, Found252.0623.
89e90 C); IR (nujol) 1644 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d
¼7.47
ꢀ
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(ddd, J¼7.9, 4.9, 0.9 Hz, 1H), 7.51 (d, J¼8.7 Hz, 2H), 7.78 (d, J¼8.7 Hz,
2H), 8.11 (ddd, J¼7.9, 2.3, 1.7 Hz, 1H), 8.83 (dd, J¼4.9, 1.7 Hz, 1H),
4.1.30. 2-Thieyl p-trifluoromethylphenyl ketone. Mp 103e104 ꢀC
(lit.39 not shown); IR (nujol) 1629 cmꢁ1; 1H NMR (400 MHz, CDCl3)
€
8.98 (dd, J¼2.3, 0.9 Hz, 1H); 13C NMR (100 MHz, CDCl3)
d¼123.5,
d
¼7.19 (dd, J¼4.9, 3.9 Hz, 1H), 7.63 (dd, J¼3.9, 1.1 Hz, 1H), 7.75e7.80
129.0, 131.4, 132.8, 134.9, 137.1, 139.8, 150.8, 153.1, 193.6.
(m, 3H), 7.96 (d, J¼7.9 Hz, 2H); 13C NMR (100 MHz, CDCl3)
¼123.6
d
(q, JCeF¼272.8 Hz), 125.5 (q, JCeF¼3.8 Hz), 128.2, 129.3, 133.6 (q,
4.1.22. p-Chlorophenyl 2-thieyl ketone. Mp 97e101 ꢀC (lit.24 mp
JCeF¼32.7 Hz), 135.1, 135.3, 141.2, 143.0, 187.0; 19F NMR (471 MHz,
93e95 C); IR (Nujol) 1630 cmꢁ1; 1H NMR (500 MHz, CDCl3)
d¼7.17
CDCl3)
d¼ꢁ62.9.
ꢀ
€
(dd, J¼4.9, 3.7 Hz,1H), 7.48 (d, J¼8.6 Hz, 2H), 7.62 (dd, J¼3.7, 1.2 Hz, 1H),
7.74 (dd, J¼4.9, 1.2 Hz, 1H), 7.82 (d, J¼8.6 Hz, 2H); 13C NMR (125 MHz,
4.1.31. Heptyl octyl ketone. Mp 36e37 C; IR (nujol) 1719 cmꢁ1; 1H
NMR (400 MHz, CDCl3)
¼0.85e0.90 (m, 6H), 1.20e1.34 (m, 18H),
1.50e1.61 (m, 4H), 2.35e2.41 (m, 4H); 13C NMR (100 MHz, CDCl3)
ꢀ
€
CDCl3)
d¼128.0, 128.7, 130.6, 134.5, 134.7, 136.4, 138.7, 143.2, 186.9.
d
4.1.23. Heptyl pꢁ-t1rifluoromethylphenyl ketone. Mp 28e31 ꢀC; IR
d
¼14.05, 14.07, 22.59, 22.63, 23.9 (2C), 29.07, 29.13, 29.22, 29.26,
1H NMR (500 MHz, CDCl3)
d
¼0.89 (t, J¼6.9 Hz,
29.4, 31.7, 31.8, 42.8 (2C), 211.8; HRMS (APCI) Calcd for C16H33O
€
(nujol) 1698 cm
;
3H), 1.25e1.42 (m, 8H), 1.75 (quint, J¼7.5 Hz, 2H), 2.99 (t, J¼7.5 Hz,
[MþH]þ 241.2526, Found 241.2525.
2H), 7.73 (d, J¼8.3 Hz, 2H), 8.06 (d, J¼8.3 Hz, 2H); 13C NMR
(125 MHz, CDCl3)
d
¼14.1, 22.6, 24.1, 29.1, 29.2, 31.7, 38.9, 124.7 (q,
4.1.32. Octyl cyclohexyl ketone. Colorless oil (lit.42 oil); IR (neat)
1709 cmꢁ1 1H NMR (500 MHz, CDCl3)
JCeF¼272.3 Hz),125.6 (q, JCeF¼3.6 Hz),128.3,134.2 (q, JCeF¼32.4 Hz),
;
d
¼0.89 (t, J¼6.9 Hz, 3H),
139.7, 199.5; 19F NMR (471 MHz, CDCl3)
d
¼ꢁ63.0; HRMS (APCI)
1.14e1.38 (m, 15H), 1.54 (quint, J¼7.5 Hz, 2H), 1.64e1.69 (m, 1H),
1.75e1.85 (m, 4H), 2.29e2.36 (tt, J¼11.2, 3.4 Hz, 1H), 2.41 (t,
Calcd for C15H20OF3 [MþH]þ 273.1461, Found 273.1465.
J¼7.5 Hz, 2H); 13C NMR (125 MHz, CDCl3)
¼14.0, 22.6, 23.7, 25.7,
d
4.1.24. Cyclohexyl p-trifluoromethylphenyl ketone. Colorless oil
25.8, 28.5, 29.1, 29.3, 29.4, 31.8, 40.6, 50.8, 214.4; HRMS (APCI) Calcd
(lit.37 oil); IR (nujol) 1692 cm
;
1H NMR (400 MHz, CDCl3)
for C15H29O [MþH]þ 225.2213, Found 225.2209.
ꢁ1
€
d
¼1.22e1.33 (m, 1H), 1.34e1.56 (m, 4H), 1.71e1.79 (m, 1H),
1.82e1.93 (m, 4H), 3.25 (tt, J¼11.1, 3.2 Hz,1H), 7.73 (d, J¼8.2 Hz, 2H),
4.1.33. t-Butyl octyl ketone. Colorless oil (lit.43 oil); IR (neat)
8.03 (d, J¼8.2 Hz, 2H); 13C NMR (125 MHz, CDCl3)
d¼25.7, 25.8, 29.2,
1708 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d
¼0.88 (t, J¼7.0 Hz, 3H), 1.13
45.9, 123.6 (q, JCeF¼272.3 Hz), 125.6 (q, JCeF¼3.6 Hz), 128.5, 134.0 (q,
(s, 9H), 1.21e1.32 (m, 10H), 1.54 (quint, J¼7.3 Hz, 2H), 2.47 (t,
JCeF¼32.4 Hz), 139.1, 202.8; 19F NMR (471 MHz, CDCl3)
d¼ꢁ63.0.
J¼7.3 Hz, 2H); 13C NMR (100 MHz, CDCl3)
¼14.1, 22.6, 23.9, 26.4,
d
29.2, 29.3, 29.5, 31.8, 36.4, 44.1, 216.2.
4.1.25. t-Butyl p-trifluoromethylphenyl ketone. Colorless oil (lit.38
oil); IR (neat) 1685 cmꢁ1
;
1H NMR (500 MHz, CDCl3)
d¼1.34
4.1.34. Octyl p-tꢁo1lyl ketone. Mp 36e37 ꢀC (lit.44 mp. 37 ꢀC); IR
(s, 9H), 7.67 (d, J¼8.3 Hz, 2H), 7.73 (d, J¼8.3 Hz, 2H); 13C NMR
(nujol) 1689 cm
;
1H NMR (400 MHz, CDCl3)
d
¼0.88 (t, J¼7.0 Hz,
€
(125 MHz, CDCl3)
d
¼27.6, 44.4, 123.7 (q, JCeF¼272.3 Hz), 125.1 (q,
3H), 1.23e1.41 (m, 10H), 1.72 (quint, J¼7.3 Hz, 2H), 2.41 (s, 3H), 2.93
JCeF¼3.6 Hz), 127.8, 132.2 (q, JCeF¼32.4 Hz), 142.1, 208.9; 19F NMR
(t, J¼7.3 Hz, 2H), 7.25 (d, J¼7.9 Hz, 2H), 7.86 (d, J¼7.9 Hz, 2H); 13C
(471 MHz, CDCl3)
d¼ꢁ62.9.
NMR (100 MHz, CDCl3)
d
¼14.1, 21.6, 22.6, 24.5, 29.2, 29.39, 29.43,
31.8, 38.5, 128.2, 129.2, 134.6, 134.5, 200.3.
4.1.26. p-Anisyl p-trifluoromethylphenyl ketone. Mp 120e124 ꢀC
(lit.39 mp. 118.9e119.4 ꢀC); IR (nujol) 1644 cmꢁ1
;
1H NMR
4.1.35. p-Anisyl octyl ketone. Mp 43e44 C; IR (nujol) 1685 cm
;
ꢁ1
ꢀ
€
€
(500 MHz, CDCl3)
d
¼3.90 (s, 3H), 6.98 (d, J¼8.9 Hz, 2H), 7.74 (d,
1H NMR (500 MHz, CDCl3)
d
¼0.88 (t, J¼7.1 Hz, 3H), 1.23e1.40 (m,
J¼8.3 Hz, 2H), 7.80e7.86 (m, 4H); 13C NMR (125 MHz, CDCl3)
10H), 1.71 (quint, J¼7.5 Hz, 2H), 2.90 (t, J¼7.5 Hz, 2H), 3.87 (s, 3H),
d
¼55.5, 113.8, 123.7 (q, JCeF¼272.3 Hz), 125.2 (q, JCeF¼3.6 Hz), 129.3,
6.93 (d, J¼8.9 Hz, 2H), 7.94 (d, J¼8.9 Hz, 2H); 13C NMR (125 MHz,
129.8, 132.6, 133.2 (q, JCeF¼33.6 Hz), 141.5, 163.7, 194.2; 19F NMR
CDCl3)
d
¼14.1, 22.6, 24.6, 29.2, 29.42, 29.44, 31.8, 38.3, 55.4, 113.6,
(471 MHz, CDCL3)
d
¼ ꢁ62.9.
130.1, 130.3, 163.2, 199.3; HRMS (APCI) Calcd for C16H25O2 [MþH]þ
249.1849, Found 249.1844.
4.1.27. p-Fluorophenyl
p-triꢀfluoromethylphenyl
ketone. Mp
;
40
ꢁ1
45
99e100 ꢀC (lit. mp. 100e101 C); IR (nujol) 1651 cm
1H NMR
4.1.36. p-Fluorophenyl octyl ketone. Mp 34 ꢀC (lit. oil); IR (nujol)
€
€
(500 MHz, CDCl3)
d¼7.19 (t, J¼8.6 Hz, 2H), 7.76 (d, J¼8.0 Hz, 2H),
1692 cmꢁ1
;
1H NMR (500 MHz, CDCl3)
d
¼0.88 (t, J¼7.2 Hz, 3H),

S. Dohi et al. / Tetrahedron 68 (2012) 6557e6564
6563
1.21e1.41 (m, 10H), 1.72 (quint, J¼7.5 Hz, 2H), 2.93 (t, J¼7.5 Hz, 2H),
7.12 (t, J¼8.6 Hz, 2H), 7.99 (dd, J¼8.6, 5.4 Hz, 2H); 13C NMR
1H), 1.34e1.55 (m, 7H), 1.71e1.79 (m, 1H), 1.82e1.94 (m, 4H), 3.26
(tt, J¼11.1, 3.2 Hz, 1H), 4.41 (q, J¼7.3 Hz, 2H), 7.98 (d, J¼8.8 Hz, 2H),
(125 MHz, CDCl3)
d
¼14.1, 22.6, 24.3, 29.1, 29.3, 29.4, 31.8, 38.5, 115.6
8.12 (d, J¼8.8 Hz, 2H); 13C NMR (100 MHz, CDCl3)
¼14.2, 25.7, 25.9,
d
(d, JCeF¼21.6 Hz),130.6 (d, JCeF¼8.4 Hz),133.5 (d, JCeF¼2.4 Hz),165.6
29.2, 45.9, 61.3, 128.1, 129.7, 133.8, 139.6, 165.8, 203.4; HRMS (APCI)
(d, JCeF¼254.3 Hz), 198.9; 19F NMR (471 MHz, CDCl3)
d¼ꢁ105.7.
Calcd for C16H21O3 [MþH]þ 261.1485, Found 261.1480.
4.1.37. p-Chlorophenyl octꢁy1l ketone. Mp 58e59 ꢀC (lit.46 colorless
4.1.46. Ethyl p-pivaloylbenzoate. Colorless oil (lit.48 oil); IR (neat)
1H NMR (400 MHz, CDCl3)
d¼0.88 (t,
1682, 1719 cmꢁ1; 1H NMR (500 MHz, CDCl3)
d
¼1.33 (s, 9H), 1.41 (t,
€
solid); IR (nujol) 1694 cm
;
J¼7.2 Hz, 3H), 1.22e1.41 (m, 10H), 1.72 (quint, J¼7.5 Hz, 2H), 2.92 (t,
J¼7.2 Hz, 3H), 4.40 (q, J¼7.2 Hz, 2H), 7.66 (d, J¼8.6 Hz, 2H), 8.07 (d,
J¼7.5 Hz, 2H), 7.43 (d, J¼8.6 Hz, 2H), 7.90 (d, J¼8.6 Hz, 2H); 13C NMR
J¼8.6 Hz, 2H); 13C NMR (125 MHz, CDCl3)
¼14.3, 27.7, 44.3, 61.3,
d
(100 MHz, CDCl3)
128.9, 129.5, 135.4, 139.2, 199.3.
d
¼14.1, 22.6, 24.3, 29.1, 29.3, 29.4, 31.8, 38.6,
127.3, 129.2, 132.0, 142.8, 165.8, 209.5.
ꢀ
€
4.1.47. Ethyl p-(methylbenzoyl)benzoate. Mp 73e74 C; IR (nujol)
4.1.38. Octyl p-ꢁtr1ifluoromethylphenyl ketone. Mp 35e37 ꢀC; IR
1650,1711 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d
¼1.43 (t, J¼7.3 Hz, 3H),
€
(nujol) 1699 cm
;
1H NMR (500 MHz, CDCl3)
d
¼0.88 (t, J¼7.2 Hz,
2.45 (s, 3H), 4.43 (q, J¼7.3 Hz, 2H), 7.30 (d, J¼8.2 Hz, 2H), 7.72 (d,
3H), 1.23e1.42 (m, 10H), 1.74 (quint, J¼7.5 Hz, 2H), 2.98 (t, J¼7.5 Hz,
J¼8.2 Hz, 2H), 7.82 (d, J¼8.6 Hz, 2H), 8.15 (d, J¼8.6 Hz, 2H); 13C NMR
2H), 7.73 (d, J¼8.0 Hz, 2H), 8.06 (d, J¼8.0 Hz, 2H); 13C NMR
(100 MHz, CDCl3)
d
¼14.3, 21.7, 61.4, 129.1, 129.4, 129.6, 130.3, 133.3,
(125 MHz, CDCl3)
d
¼14.1, 22.6, 24.1, 29.1, 29.3, 29.4, 31.8, 38.9, 123.6
134.3, 141.6, 143.9, 165.9, 195.8; HRMS (APCI) Calcd for C17H17O3
(q, JCeF¼272.3 Hz), 125.6 (q, JCeF¼3.6 Hz), 128.3, 134.2 (q,
[MþH]þ 269.1172, Found 269.1167.
JCeF¼32.4 Hz), 139.7, 199.5; 19F NMR (471 MHz, CDCl3)
¼ꢁ63.0;
d
HRMS (APCI) Calcd for C16H22F3O [MþH]þ 287.1617, Found 287.1617.
4.1.48. Ethyl p-(trifluorꢁom1 ethylbenzoyl)benzoate. Mp 81e82 ꢀC; IR
€
(nujol) 1651, 1718 cm
;
1H NMR (500 MHz, CDCl3)
d
¼1.44 (t,
4.1.39. Octyl 3-pyridyl ketone. Colorless oil; IR (neat) 1691 cmꢁ1; 1H
J¼7.2 Hz, 3H), 4.44 (q, J¼7.2 Hz, 2H), 7.78 (t, J¼8.3 Hz, 2H), 7.85 (d,
NMR (400 MHz, CDCl3)
d
¼0.88 (t, J¼7.0 Hz, 3H), 1.22e1.44 (m, 10H),
J¼8.3 Hz, 2H), 7.91 (d, J¼8.3 Hz, 2H), 8.02 (d, J¼8.3 Hz, 2H); 13C NMR
1.75 (quint, J¼7.3 Hz, 2H), 2.99 (t, J¼7.3 Hz, 2H), 7.43 (ddd, J¼7.9, 4.8,
(125 MHz, CDCl3)
d¼14.2, 61.5, 123.5 (q, JCeF¼272.6 Hz), 125.5 (q,
0.9 Hz,1H), 8.24 (ddd, J¼7.9, 2.3,1.8Hz,1H), 8.78(dd, J¼4.8,1.8 Hz,1H),
JCeF¼3.6 Hz), 129.6, 129.8, 130.2, 134.11 (q, JCeF¼32.7 Hz), 134.14,
9.17 (dd, J¼2.3, 0.9 Hz, 1H); 13C NMR (100 MHz, CDCl3)
d¼14.1, 22.6,
140.0, 140.1, 165.6, 194.9; 19F NMR (471 MHz, CDCl3)
d
¼ꢁ62.9;
24.0, 29.1, 29.2, 29.4, 31.8, 38.9, 123.6, 132.2, 135.4, 149.6, 153.3, 199.3;
HRMS (APCI) Calcd for C17H14O3F3 [MþH]þ 323.0890, Found
HRMS (APCI) Calcd for C14H22ON [MþH]þ 220.1696, Found 220.1693.
323.0887.
4.1.40. Octyl 2-thieyl ketone. Colorless oil; IR (neat) 1663 cmꢁ1; 1H
4.1.49. p-Cyanophenyl hepyl ketone. Mp 38e39 C; IR (nujol) 1698,
2233 cmꢁ1 1H NMR (500 MHz, CDCl3)
ꢀ
€
NMR (400 MHz, CDCl3)
d
¼0.88 (t, J¼7.0 Hz, 3H), 1.22e1.42 (m, 10H),
;
d
¼0.89 (t, J¼6.9 Hz, 3H),
1.74 (quint, J¼7.5 Hz, 2H), 2.89 (t, J¼7.5 Hz, 2H), 7.12 (dd, J¼4.9,
1.25e1.41 (m, 8H), 1.74 (quint, J¼7.5 Hz, 2H), 2.98 (t, J¼7.5 Hz, 2H),
3.6 Hz, 1H), 7.62 (dd, J¼4.9, 1.1 Hz, 1H), 7.71 (dd, J¼3.6, 1.1 Hz, 1H);
7.77 (d, J¼8.6 Hz, 2H), 8.04 (d, J¼8.6 Hz, 2H); 13C NMR (125 MHz,
13C NMR (100 MHz, CDCl3)
d¼14.1, 22.6, 24.8, 29.1, 29.3, 29.4, 31.8,
CDCl3)
d
¼14.1, 22.6, 24.0, 29.1, 29.2, 31.6, 38.9, 116.1, 118.0, 128.4,
39.4, 128.0, 131.6, 133.3, 144.5, 193.6; HRMS (APCI) Calcd for
132.5, 139.9, 199.1; HRMS (APPI) Calcd for C15H19ON [M]þ 229.1461,
Found 229.1462.
C13H21OS [MþH]þ 225.1308, Found 225.1303.
4.1.41. Heptyl cyclohexyl ketone. Colorless oil (lit.42 oil); IR (neat)
4.1.50. p-Cyanophenyl cyclohexyl ketone. Mp 59e60 ꢀC (lit.37 oil); IR
ꢁ1
1709 cmꢁ1
;
1H NMR (500 MHz, CDCl3)
d
¼0.88 (t, J¼7.2 Hz, 3H),
(nujol) 1685, 2227 cm
;
1H NMR (500 MHz, CDCl3)
d
¼1.23e1.32
€
1.14e1.37 (m, 13H), 1.54 (quint, J¼7.2 Hz, 2H), 1.63e1.69 (m, 1H),
(m, 1H), 1.35e1.54 (m, 4H), 1.72e1.79 (m, 1H), 1.83e1.91 (m, 4H),
3.23 (tt, J¼11.2, 3.2 Hz, 1H), 7.77 (d, J¼8.6 Hz, 2H), 8.12 (d, J¼8.6 Hz,
1.75e1.85 (m, 4H), 2.33 (tt, J¼11.2, 3.4 Hz,1H), 2.42 (t, J¼7.2 Hz, 2H);
13C NMR (125 MHz, CDCl3)
d
¼14.1, 22.6, 23.7, 25.7, 25.8, 28.5, 29.1,
2H); 13C NMR (125 MHz, CDCl3)
128.6, 132.5, 139.4, 202.4.
d
¼25.7, 25.8, 29.1, 45.9, 115.9, 118.0,
29.3, 31.7, 40.6, 50.8, 214.5; HRMS (APCI) Calcd for C14H27O [MþH]þ
211.2056, Found 211.2056.
4.1.51. p-Cyanophenyl p-tolyl ketone. Mpꢁ1160e162 ꢀC (lit.49 mp
;
1H NMR (400 MHz,
ꢀ
€
4.1.42. Dicyclohexyl ketone. Colorless oil (commercial, oil); IR
160e160 C); IR (Nujol) 1650, 2229 cm
(neat) 1704 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d
¼1.12e1.38 (m, 10H),
1.62e1.69 (m, 2H), 1.71e1.83 (m, 8H), 2.48 (tt, J¼11.1, 2.9 Hz, 2H);
13C NMR (100 MHz, CDCl3)
¼25.6, 25.8, 28.5, 49.1, 217.0.
CDCl3)
d
¼2.46 (s, 3H), 7.31 (d, J¼7.9 Hz, 2H), 7.70 (d, J¼8.2 Hz, 2H),
7.78 (d, J¼8.6 Hz, 2H), 7.85 (d, J¼8.6 Hz, 2H); 13C NMR (100 MHz,
d
CDCl3)
144.4, 194.7.
d
¼21.7, 115.4, 118.0, 129.3, 130.1, 130.3, 132.1, 133.6, 141.6,
4.1.43. t-Butyl cyclohexyl ketone. Colorless oil. (lit.47 oil); IR (neat)
1701 cmꢁ1; 1H NMR (500 MHz, CDCl3)
¼1.14 (s, 9H), 1.21e1.46 (m,
5H),1.58e1.70 (m, 3H),1.73e1.80 (m, 2H), 2.84 (tt, J¼11.5, 3.4 Hz,1H);
13C NMR (125 MHz, CDCl3)
¼25.7, 25.8, 26.0, 29.9, 44.6, 44.9, 218.9.
d
4.1.52. p-Cyanophenyl
p-trifluoromethylphenyl
ketone. Mp
ꢁ1
85e86 ꢀC; IR (nujol) 1655, 2239 cm
;
1H NMR (500 MHz, CDCl3)
€
d
d
¼7.80 (d, J¼8.3 Hz, 2H), 7.83 (d, J¼8.6 Hz, 2H), 7.88e7.92
(m, 4H); 13C NMR (125 MHz, CDCl3)
d
¼116.3, 117.8, 124.5
ꢀ
€
4.1.44. Ethyl p-octanoylbenzoate. Mp 56e57 C; IR (nujol) 1682,
(q, JCeF¼272 Hz), 125.7 (q, JCeF¼3.6 Hz), 130.2, 130.3, 132.4, 134.5
1728 cmꢁ1 1H NMR (500 MHz, CDCl3)
;
d
¼0.89 (t, J¼7.2 Hz, 3H),
(q, JCeF¼32.4 Hz), 139.3, 140.1, 193.9; 19F NMR (471 MHz, CDCl3)
1.25e1.45 (m, 11H), 1.74 (quint, J¼7.2 Hz, 2H), 2.99 (t, J¼7.2 Hz, 2H),
4.41 (q, J¼7.2 Hz, 2H), 8.00 (d, J¼8.3 Hz, 2H), 8.12 (d, J¼8.3 Hz, 2H);
d
¼ꢁ63.0; HRMS (APCI) Calcd for C15H8ONF3 [M]ꢁ 275.0563,
Found 275.0567.
13C NMR (125 MHz, CDCl3)
d
¼14.1, 14.3, 22.6, 24.1, 29.1, 29.2, 31.7,
ꢀ
€
39.0, 61.4, 127.9, 129.7, 134.0, 140.1, 165.8, 200.1; HRMS (APCI) Calcd
4.1.53. o-Nitrophenyl p-tolyl ketone. Mp 152e154 C; IR (nujol)
for C17H25O3 [MþH]þ 277.1798, Found 277.1794.
1351, 1523, 1668 cmꢁ1 1H NMR (500 MHz, CDCl3)
;
d
¼2.41 (s, 3H),
7.25 (d, J¼8.3 Hz, 2H), 7.48 (dd, J¼7.5, 1.4 Hz, 1H), 7.63e7.69 (m, 3H),
4.1.45. Ethyl p-(cyclohexanecarbonyl)benzoate. Mp 46e48 ꢀC; IR
7.77 (dt, J¼7.5, 1.4 Hz, 1H), 8.22 (dd, J¼7.5, 1.4 Hz, 1H); 13C NMR
(neat) 1685, 1720 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d
¼1.21e1.33 (m,
(125 MHz, CDCl3)
d
¼21.7, 124.4, 128.9, 129.4, 129.5, 130.4, 133.4,

6564
S. Dohi et al. / Tetrahedron 68 (2012) 6557e6564
Angew. Chem., Int. Ed. 1996, 35, 1700; (d) Guijarro, A.; Rosenberg, D. M.; Rieke,
R. D. J. Am. Chem. Soc. 1999, 121, 4155; (e) Kim, S. H.; Rieke, R. D. J. Org. Chem.
2000, 65, 2322; (f) Dohle, W.; Kopp, F.; Gahiez, G.; Knochel, P. Synlett 2001,
134.1, 136.3, 144.9, 146.6, 193.1; HRMS (APCI) Calcd for C14H12O3N
[MþH]þ 242.0812, Found 242.0810.
€
ꢀ
1901; (g) Furstner, A.; Leitner, A.; Mendez, M.; Krause, H. J. Am. Chem. Soc. 2002,
4.1.54. o-Nitrophenyl p-nitrophenyl ketone. Mp 198e200 ꢀC; IR
€
124, 13856; (h) Furstner, A.; De Souza, D.; Parra-Parado, L.; Jensen, J. T. Angew.
ꢀ
ꢁ1
Chem., Int. Ed. 2003, 42, 5358; (i) Fillon, H.; Gosmini, C.; Perichon, J. J. Am. Chem.
€
(nujol) 1687, 1520, 1351 cm
;
1H NMR (500 MHz, CDCl3)
d¼7.54
Soc. 2003, 125, 3867; (j) Knochel, P.; Dohle, W.; Gommermann, N.; Kneisel, F. F.;
Kopp, F.; Korn, T.; Sapountzis, I.; Vu, V. A. Angew. Chem., Int. Ed. 2003, 42, 4302;
(dd, J¼7.5, 1.4 Hz, 1H), 7.78 (dt, J¼7.5, 1.4 Hz, 1H), 7.87 (dt, J¼7.5,
1.4 Hz, 1H), 7.91 (d, J¼9.2 Hz, 2H), 8.29e8.33 (m, 3H); 13C NMR
€
(k) Scheiper, B.; Bonnekessel, M.; Krause, H.; Furstner, A. J. Org. Chem. 2004, 69,
€
3943; (l) Sherry, B. D.; Furstner, A. Acc. Chem. Res. 2008, 41, 1500.
(125 MHz, CDCl3)
d
¼124.0, 124.7, 128.8, 129.9, 131.3, 134.7, 135.0,
13. (a) Wakefield, B. J. Organomagnesium Methods in Organic Synthesis; Academic:
London, 1995; (b) Silverman, G. S.; Rakita, P. E. Handbook of Grignard Reagents;
Marcel Dekker: New York, NY, 1996.
140.5, 146.5, 150.6, 191.7; HRMS (APCI) Calcd for C13H8O5N2 [M]ꢁ
272.0439, Found 272.0440.
14. (a) Ball, S. C.; Davies, R. P.; Raithby, P. R.; Shields, G. P.; Snaith, R. J. Organomet.
Chem. 1998, 554, 457; (b) Clegg, W.; Davies, R. P.; Dunbar, L.; Feeder, N.; Liddle,
S. T.; Mulvey, R. E.; Sanith, R.; Wheatley, A. E. H. Chem. Commun. 1999, 1401.
15. Nahm, S.; Weinreb, S. M. Tetrahedron Lett. 1981, 22, 3815.
4.1.55. 2-Nitro-4-benzoylphenyl p-tolyl ketone. Mp 141e142 ꢀC; IR
(nujol) 1352, 1534, 1662 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d
¼2.43 (s,
€
16. Gowda, M. S.; Pande, S. S.; Ramakrishna, R. A.; Prabhu, K. R. Org. Biomol. Chem.
3H), 7.28 (d, J¼8.6 Hz, 2H), 7.57 (t, J¼7.9 Hz, 2H), 7.61 (d, J¼7.7 Hz,
2011, 9, 5365.
1H), 7.66e7.72 (m, 3H), 7.85 (dd, J¼7.9, 1.4 Hz, 2H), 8.18 (dd, J¼7.7,
17. Hirao, T.; Misu, D.; Agawa, T. J. Am. Chem. Soc. 1985, 107, 7179.
18. Reviews: (a) Togo, H.; Iida, S. Synlett 2006, 2159; (b) Togo, H. J. Synth. Org. Chem.
2008, 66, 652.
1.1 Hz,1H), 8.61 (d, J¼1.1 Hz,1H); 13C NMR (100 MHz, CDCl3)
¼21.8,
d
125.6, 128.9, 129.2, 129.5, 129.6, 130.0, 133.0, 133.6, 134.8, 135.9,
139.3, 139.7, 145.4, 146.6, 192.3, 193.5; HRMS (APCI) Calcd for
C21H16O4N [MþH]þ 346.1074, Found 346.1065.
19. Ushijima, S.; Dohi, S.; Moriyama, K.; Togo, H. Tetrahedron 2012, 68, 1436.
20. (a) Mori, N.; Togo, H. Synlett 2004, 880; (b) Mori, N.; Togo, H. Synlett 2005,
1456; (c) Mori, N.; Togo, H. Tetrahedron 2005, 61, 5915; (d) Ishihara, M.; Togo, H.
Synlett 2006, 227; (e) Iida, S.; Togo, H. Synlett 2006, 2633; (f) Ishihara, M.; Togo,
H. Tetrahedron 2007, 63, 1474; (g) Iida, S.; Togo, H. Tetrahedron 2007, 63, 8274;
(h) Iida, S.; Togo, H. Synlett 2007, 407; (i) Iida, S.; Togo, H. Synlett 2008, 1639; (j)
Iida, S.; Ohmura, R.; Togo, H. Tetrahedron 2009, 65, 6257; (k) Moroda, A.;
Furuyama, S.; Togo, H. Synlett 2009, 1336; (l) Ushijima, S.; Togo, H. Synlett 2010,
1067; (m) Furuyama, S.; Togo, H. Synlett 2010, 2325; (n) Baba, H.; Togo, H.
Tetrahedron Lett. 2010, 51, 2063; (o) Ushijima, S.; Togo, H. Synlett 2010, 1562; (p)
Ushijima, S.; Moriyama, K.; Togo, H. Tetrahedron 2011, 67, 958; (q) Ishii, G.;
Moriyama, K.; Togo, H. Tetrahedron Lett. 2011, 52, 2404; (r) Baba, H.; Moriyama,
K.; Togo, H. Tetrahedron Lett. 2011, 52, 4303; (s) Suzuki, Y.; Yoshino, T.;
Moriyama, K.; Togo, H. Tetrahedron 2011, 67, 3809; (t) Suzuki, Y.; Moriyama, K.;
Togo, H. Tetrahedron 2011, 67, 7956; (u) Baba, H.; Moriyama, K.; Togo, H. Synlett
2012, 1175.
Acknowledgements
Financial support in the form of a Grant-in-Aid for Scientific
Research (No. 20550033) from the Ministry of Education, Culture,
Sports, Science, and Technology in Japan and Iodine Research
Project in Chiba University is gratefully acknowledged.
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