NNN pincer Ru(II)-complex-catalyzed α-alkylation of ketones with alcohols

Article abstract of DOI:10.1021/acs.joc.8b00013

A series of novel ruthenium(II) complexes supported by a symmetrical NNN ligand were prepared and fully characterized. These complexes exhibited good performance in transfer hydrogenation to form new C-C bonds using alcohols as the alkylating agents, generating water as the only byproduct. A broad range of substrates, including (hetero)aryl- or alkyl-ketones and alcohols, were well tolerated under the optimized conditions. Notably, α-substituted methylene ketones were also investigated, which afforded α-branched steric hindrance products. A potential application of α-alkylation of methylene acetone to synthesize donepezil was demonstrated, which provided the desired product in 83% yield. Finally, this catalytic system could be applied to a one-pot double alkylation procedure with sequential addition of two different alcohols. The current protocol is featured with several characteristics, including a broad substrate scope, low catalyst (0.50 mol %) loadings, and environmental benignity.

Full text of DOI:10.1021/acs.joc.8b00013

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NNN Pincer Ru(II)-Complex-Catalyzed #-Alkylation of Ketones with Alcohols
Xiao-Niu Cao, Xiao-Min Wan, Fa-Liu Yang, Ke Li, Xin-Qi Hao, Tian Shao, Xinju Zhu, and Mao-Ping Song
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b00013 • Publication Date (Web): 13 Mar 2018
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The Journal of Organic Chemistry
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NNN Pincer Ru(II)-Complex-Catalyzed α‑Alkylation of Ketones with Al-
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cohols
Xiao-Niu Cao,a Xiao-Min Wan,a Fa-Liu Yang,a Ke Li,b Xin-Qi Hao,a Tian Shao,*a Xinju Zhu,*a and
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Mao-Ping Songa
aCollege of Chemistry and Molecular Engineering, School of Life Sciences, Zhengzhou University, No. 100 of Science Road,
Zhengzhou, Henan 450001, P. R. China
bShandong Qiaochang Modern Agriculture Co., Ltd, No. 1181 Huanghe 12 Road, Binzhou, Shandong 256600, P. R. China
ABSTRACT: A series of novel ruthenium(II) complexes supported by a symmetrical NNN ligand were prepared and fully charac-
terized. These complexes exhibited good performance in transfer hydrogenation to form new C−C bonds using alcohols as the al-
kylating agents, generating water as the only byproduct. A broad range of substrates, including (hetero)aryl- or alkyl-ketones and
alcohols, were well tolerated under the optimized conditions. Notably, α-substituted methylene ketones were also investigated,
which afforded α-branched steric hindrance products. A potential application of α-alkylation of methylene acetone to synthesize
donepezil was demonstrated, which provided the desired product in 83% yield. Finally, this catalytic system could be applied to a
one-pot double alkylation procedure with sequential addition of two different alcohols. The current protocol is featured with several
characteristics, including a broad substrate scope, low catalyst (0.50 mol%) loadings, and environmental benignity.
limitation, Donohoe group have reported [Cp*RhCl2]2-
INTRODUCTION
catalyzed methylation of ketones with methanol to provide
various α-branched products.13a Later, a combination of
α-Alkylation of carbonyl compounds is a useful method for
[Ir(cod)Cl2]2 catalyst and a bulky phosphine ligand was em-
ployed to interrupt HB process, which enabled the addition of
a nucleophile to in-situ generated enone intermediates.13b Sub-
sequently, groups of Li,4c Obora,14 Andersson,15 Seayard,16 and
Liu17 have also made contributions to α-alkylations of ketones
with methanol18 to access α-branched products (Scheme 1b).
However, the alkylation agent was mostly limited to methanol,
and the utilization of other alcohols was less developed. Re-
cently, Glorius group has developed an in-situ generated Ru-
NHC complex-catalyzed high efficient α-alkylation of meth-
ylene ketones with various primary alcohols (Scheme 1c).19
Donohoe group has reported Ir complexes-catalyzed α-
alkylation of ortho-substituted phenyl ketones with primary20a
and secondary20b alcohols to give α- and β-branched steric
hindrance products, respectively. Moreover, another Ru(II)-
catalyzed three-component coupling reaction between ketones,
methanol, and primary alcohols has also been investigated.21
the construction of C−C bonds in organic chemistry, which
provides valuable access to various functionalized organic
compounds with applications in agrochemicals, pharmaceuti-
cals, and material sciences. Traditionally, the formation of
C−C bonds was achieved using enolates, organometallic rea-
gents or alkyl halides, which usually produced stoichiometric
amounts of undesirable salts.1 Recently, transition-metal-
catalyzed hydrogen borrowing (HB) or hydrogen autotransfer
(HA) strategy has emerged as an appealing alternative to form
C−C bonds.2 Such methodology is more atom-economical and
environmentally benign due to the utilization of readily avail-
able alcohols and formation of water as the sole byproduct.
To date, a variety of transition-metal catalysts, including
Ru,3 Ir,4 Pd,5 Os,6 Fe,7 Co,8 and Mn,9 have been developed for
α-alkylation of ketones. Other challenging carbonyl substrates,
such as esters8a,10 and amides,11 have also been investigated. In
addition, α-alkylations of ketones with alcohols could be suc-
cessfully achieved under metal-free conditions.12 Despite
above achievements, most ketone substrates are limited to
methyl ketones, which underwent monoalkylation with alco-
hols to generate linear ketones (Scheme 1a). To overcome this
To obtain efficient and selective catalytic activity with
broad functional tolerance, pincer-type complexes have re-
ceived much attention in recent years. Through fine modifica-
tions of steric and electronic effects of ligand precursors, pin-
cer metal catalysts demonstrated wide applications in
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(de)hydrogenation and transfer (de)hydrogenation reactions.22
light, α-alkylated product 5a was obtained in 92% yield cata-
lyzed by pincer Ru complex b (Table 1, entry 2). Subsequently,
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Our group have reported a series of chiral symmetrical and
unsymmetrical pincer complexes,23 including NNN pincer Ru
complexes with high efficiency in transfer hydrogenation of
ketones and N-monoalkylation of Amines with alcohols.24 As
part of our ongoing effort in this field, we herein synthesized
three new NNN pincer Ru complexes a-c and investigated
their application in α-alkylation of ketones (Scheme 1d). Es-
pecially, α-alkylation of methylene ketones could be success-
fully accessed to deliver α-branched products in high yields.
Moreover, this pincer Ru-catalyzed α-alkylation of methylene
ketones could be utilized to synthesize donepezil, a representa-
tive drug for the treatment of Alzheimer’s disease, in 83%
yield. Compared with previous reports, this methodology re-
quires less catalyst (0.5 mol%) and base (0.15−0.5 equiv)
loadings, as well as a shorter reaction time (4−12 h).
various bases and solvents were screened (Table S2 and S3),
t
which indicates that K3PO4·3H2O and amyl alcohol were the
optimal choice (Table 1, entry 2). Decreasing the volume of
tamyl alcohol to 0.5 mL further improved the production of 5a
in 97% yield (Table 1, entry 12). When 0.10 equiv
K3PO4·3H2O or 0.40 mmol 4a was individually employed to
catalytic system, a decreased yield of 63% and 90% was ob-
tained, respectively (Table 1, entries 13 and 14). Finally, in the
absence of catalyst b or K3PO4·3H2O, no desired product or
trace amount of 5a, if any, was detected for α-alkylation of
acetophenone (Table 1, entries 15 and 16).
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Table 1. Optimization of Reaction Conditionsa
Scheme 1. Different α-alkylation methods.
5a
Yield (%)
entry
catalyst
base
solvent
a
b
c
K3PO4·3H2O
K3PO4·3H2O
K3PO4·3H2O
K3PO4·3H2O
NaOH
tAmyl alcohol
tAmyl alcohol
tAmyl alcohol
tAmyl alcohol
tAmyl alcohol
tAmyl alcohol
tAmyl alcohol
tAmyl alcohol
toluene
1
65
92
74
90
83
55
82
66
54
29
31
97
63
90
-
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4
d
b
b
b
b
b
b
b
b
b
b
b
-
5
6
NaNH2
7
KOH
8
CsCO3
9
K3PO4·3H2O
K3PO4·3H2O
K3PO4·3H2O
K3PO4·3H2O
K3PO4·3H2O
K3PO4·3H2O
-
RESULTS AND DISCUSSION
10
11
b12
c13
d14
15
16
THF
H2O
The synthesis of the ligand precursors and NNN pincer
Ru(II) complexes a−c are summarized in Scheme 2. The lig-
and precursors 2a−b were prepared from 1 through successive
bromination with N-bromosuccinimide (NBS) and cyclization
with 2-aminopyridine derivatives. Subsequent cyclometalation
of 2 with RuCl2(PPh3)3 refluxed in toluene generated the de-
sired pincer Ru(II) products a-c in 80−82% yields. The ob-
tained complexes a−c were bench-stable and characterized by
HRMS and 1H, 13C{1H}, and 31P{1H } spectra.
tAmyl alcohol
tAmyl alcohol
tAmyl alcohol
tAmyl alcohol
tAmyl alcohol
trace
K3PO4·3H2O
aReaction conditions: 3a (0.40 mmol), 4a (0.44 mmol), Ru complex
(0.50 mol%), base (0.15 equiv), solvent (1.5 mL), 120 oC, 4 h, Ar
c
d
atmosphere. btAmyl alcohol (0.5 mL). K3PO4·3H2O (0.10 equiv). 4a
Scheme 2. Preparation of ligand precursors and NNN pincer
(0.40 mmol)
Ru(II) complexesa
With the optimized conditions in hand (Table 1, entry 12), a
broad range of alcohols was investigated (Scheme 3). Initially,
reaction between acetophenone 3a and aromatic alcohols were
examined. In most cases, both electron-donating (OMe, CH3)
and electron-withdrawing (halogen, CF3) groups at the para-,
meta-, and ortho-positions were well tolerated to provide the
desired products 5a−r in 70−98% yields. Also, disubstituted
aromatic alcohols also reacted with 3a smoothly to generate
products 5s−t in 84% and 86% yields, respectively. Subse-
quently, heteroaromatic alcohols were employed. Compared
with above cases (5a−t), products 5u−w were isolated in de-
creased yields (31−52%). In an attempt to obtain product 5u,
the over reduction of 5u was also isolated, which to some ex-
tent could explain the relatively low efficiency for certain sub-
aReaction conditions: (i) NBS, CH3CN, p-TsOH·H2O; (ii) 4-
methoxypyridin-2-amine or 4-methylpyridin-2-amine or 4-
(trifluoromethyl)pyridin-2-amine,
RuCl2(PPh3)3, toluene, reflux, 24 h.
NaHCO3,
CH3CN;
(iii)
Initially, the α-alkylation of acetophenone 3a and benzyl al-
cohol 4a was examined in the presence of obtained Ru com-
plexes a−c and d24a (R = H) as shown in Table 1. To our de-
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strates. Next, a series of aliphatic alcohols, including linear
alcohols and branched alcohols, were utilized, which afforded
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2
3
4
5
the desired products 5x−5ac in 57−83% yields. Moreover, the
current methodology could be applied to secondary alcohol to
furnish the β-branched product 5ad in 68% yield.
Scheme 3. Substrate scope of alcoholsa
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aReaction conditions: 3 (0.40 mmol), 4a (0.44 mmol), Ru complex
t
b (0.50 mol%), K3PO4·3H2O (0.15 equiv), Amyl alcohol (0.5 mL),
120 oC, 4 h, Ar atmosphere. bK3PO4·3H2O (0.50 equiv), 12 h.
tone. Initially, phenyl-substituted methylene ketone was exam-
ined. When a higher base loading (0.50 equiv) and a longer
reaction time (12 h) were employed, a wide range of primary
alcohols, including aromatic, heteroaromatic, and aliphatic
alcohols, could efficiently couple with methylene ketones to
provide α-branched products 8a−n in 53−93% yields. Subse-
quently, propiophenone was applied, which afforded products
8o−q in 60−92% yields. Finally, methylene ketones bearing a
cyclic carbon skeleton, including cyclohexanone, 1-tetralones,
and 1-indanones were also investigated for α-alkylation reac-
tion. Compared with phenyl-substituted methylene ketone and
propiophenone, cyclic ketones were more reactive, which gave
the corresponding α-branched products 8r−ad in 60-98%
yield. Importantly, the currently methodology could be uti-
lized to direct prepare a biologically active drug donepezil 8ae
in 83% yield. We also carried out alkylation of ketonic me-
thine carbon using this protocol, but no further alkylation of
product 8 was detected.
aReaction conditions: 3a (0.40 mmol), 4 (0.44 mmol), Ru complex b
(0.50 mol%), K3PO4·3H2O (0.15 equiv), tAmyl alcohol (0.5 mL), 120
oC, 4 h, Ar atmosphere. b12 h. cK3PO4·3H2O (0.50 equiv), 12 h.
To further examine the applicability of α-alkylation reaction,
the substrate of methyl ketones 3 was then explored (Scheme
4). For para- and meta-substituted acetophenone derivatives,
both electron-donating and electron-withdrawing groups re-
acted with 4a smoothly to give the desired products 6a−e in
65−99% yields. Also, α-alkylation of 1-acetonaphthone and 2-
acetonaphthone provided the corresponding products 6f−g in
80% and 96% yields, respectively. Subsequently, heteroaro-
matic methyl ketones were examined, which generated prod-
ucts 6h−i in 20% and 90% yields, respectively. Next, a series
of aliphatic methyl ketones, including linear ketones, iso-butyl
methyl ketone, and tert-butyl methyl ketone, underwent ben-
zylation site-selectively to afford products 6j−l in 73-79%
yields with increased base loading (0.50 equiv) and reaction
time (12 h).
Finally, a one-pot sequential alkylation experiment was pre-
liminary conducted under the current strategy. When two dif-
ferent alcohols, namely benzyl alcohol 4a and p-
methoxybenzyl alcohol 4b, were installed on acetophenone in
sequence, the α-branched product 9 was obtained in 23% yield,
accompanied with 5a retrieved in 17% yield (Scheme 6a). To
explain the low efficiency of one-pot sequential alkylation
methodology, several experiments were performed. In the
competitive reactions between methyl ketone 3a, methylene
ketone 5a or 7a, and alcohol 4b, the linear product 5b was
isolated in 93% and 91% yields, respectively (Scheme 6b-c).
However, the majority of methylene ketone remains unreacted,
indicating methyl ketone 3a exhibited superior α-alkylation
selectivity compared with methylene ketones 5a and 7a.
Meanwhile, for reaction between 5a and 4b, the corresponding
product 9 was obtained in 31% yield under the current reaction
conditions, accompanied with a substantial amount (52%) of
unreacted substrate 5a retrieved (Scheme 6d). Despite low
yield was achieved, this method provides facile access to α-
branched ketone derivatives. Further optimizations are still in
progress currently.
Encouraged by the above experimental results, we next
sought to α-alkylation of methylene ketones (Scheme 5),
which is less explored due to relatively low reactivity com-
pared with methyl ke-
Scheme 4. Substrate scope of methyl ketonesa
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Scheme 5. Substrate scope of methylene ketones and alcoholsa
To shed light on the reaction mechanism, a set of control ex-
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2
3
4
5
6
periments were carried out (Scheme 7). Under the standard
conditions, the coupling reaction between 3a and 10 led to
α,β-unsaturated ketone 11 in 71% yield (Scheme 7, eq a). Next,
in the presence of alcohol 4a, the corresponding intermediate
11 was further converted to the desired product 5a in 96%
yield (Scheme 7, eq b).
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Scheme 7. Control experiments
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On the basis of the above discussion and previous reports, a
plausible mechanism was proposed as shown in scheme 8.
Initially, the reaction between Ru complex b and alcohol 4 in
the presence of base generates Ru-alkoxide species I. Subse-
quently, β-hydrogen elimination of alkoxo ruthenium species I
gives rise to Ru-H species II and the aldehyde intermediate A.
Although we were unable to isolate R-H species II, the gener-
ation of R-H complexes was well documented25 and has been
verified by Yu group26 as the active catalyst for transfer hy-
drogenation. Next, the condensation reaction between inter-
mediate A and ketones (3 or 7) in the presence of K3PO4·3H2O
results in α,β-unsaturated ketone intermediate B. Finally, the
coordination and addition of Ru-H species II into the double
bond of intermediate B affords Ru species III, which reacts
with the alcohol 4 to releases the ketone products (5 or 6 or 8)
and regenerates Ru-alkoxide species I.
Scheme 8. Proposed plausible mechanism
aReaction conditions: 7 (0.40 mmol), 4 (0.44 mmol), Ru complex b
(0.50 mol%), K3PO4·3H2O (0.15 equiv), tAmyl alcohol (0.5 mL), 120
oC,
4
h, Ar atmosphere. bK3PO4·3H2O (0.50 equiv), 12 h.
cK3PO4·3H2O (0.25 equiv).
Scheme 6. One-pot sequential alkylation of acetophenone
aReaction conditions: 3a (0.40 mmol), 4a (0.44 mmol), Ru complex b
t
(0.5 mol%), K3PO4·3H2O (0.15 equiv), Amyl alcohol (0.5 mL), 120
b
oC, 4 h, Ar atmosphere. 4b (0.44 mmol), K3PO4·3H2O (0.50 equiv),
12 h. c3a (0.40 mmol), 5a (0.40 mmol), 4b (0.44 mmol), K3PO4·3H2O
(0.50 equiv), 12 h. d3a (0.40 mmol), 7a (0.40 mmol), 4b (0.44 mmol),
e
K3PO4·3H2O (0.50 equiv), 12 h. 5a (0.40 mmol), 4b (0.44 mmol),
f
g
CONCLUSION
K3PO4·3H2O (0.50 equiv), 12 h. Conversion of 5a (10%). Conver-
sion of 7a (37%). hConversion of 5a (48%)
In conclusion, we have prepared a series of novel NNN pin-
cer Ru(II) complexes, which exhibited superior catalytic activ-
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ity for α-alkylation of various ketones, including methylene
145.8, 145.0, 137.5, 136.3, 125.2, 119.3, 115.8, 115.6, 110.7,
21.4; HRMS (ESI-TOF) m/z: [M + H]+ calcd for C21H18N5
1
2
3
4
5
6
7
8
counterparts, to afford linear or branched products in moderate
to good yields using borrowing hydrogen strategy. A broad
range of alcohols, including (hetero)aromatic and aliphatic
ones, were proved to be ideal coupling partners. This protocol
enables the facile synthesis of donepezil drug in high yield
directly from commercially available materials. Finally, a one-
pot sequential alkylation was also preliminary conducted to
yield the corresponding α-branched product.
340.1557, found 340.1558.
2,6-Bis(7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-
yl)pyridine (2c). Yellowish solid (192.4 mg, 43% yield); mp:
270−272 °C; 1H NMR (400 MHz, CDCl3) δ 8.46 (s, 2H), 8.29
(d, J = 7.2 Hz, 2H), 8.18 (d, J = 7.6 Hz, 2H), 7.98 (s, 2H), 7.94
(t, J = 7.8 Hz, 1H), 6.94–7.07 (m, 2H); 13C{1H} NMR (101
MHz, CDCl3) δ 152.0, 147.9, 143.7, 137.9, 126.5, 124.6,
121.9, 120.2, 115.9, 112.2, 108.7; 19F NMR (376 MHz,
CDCl3) δ -63.68; HRMS (ESI-TOF) m/z: [M + H]+ calcd for
C21H12F6N5 448.0991, found 448.0991.
9
EXPERIMENTAL SECTION
General Information
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All reactions were carried out in oven-dried glassware under
an Ar atmosphere unless otherwise mentioned. Solvents were
dried with standard methods and freshly distilled prior to use if
needed. Melting points were determined on an XT4A melting
point apparatus and are uncorrected. Flash column chromatog-
raphy was performed using 200−300 mesh silica gel. Analyti-
cal and preparative thin-layer chromatography (TLC) plates
coated with commercial silica gel GF254 were used to monitor
General Procedure for Preparation of Ru complexes a−c
To a 50 mL Schlenk flask was added RuCl2(PPh3)3 (191.8 mg,
0.20 mmol) and compounds 2 (0.20 mmol) in toluene (20 mL).
The reaction mixture was refluxed for 24 h under an argon
atmosphere. After cooled to room temperature, the solution
was precipitated to form a microcrystalline solid. The solid
was filtered off, recrystallization from methylene chloride and
petroleum ether, and dried under reduced pressure to afford
the corresponding Ru complexes a−c.
1
the reactions and purify products. H NMR and 13C{H} NMR
spectra were recorded at 400 MHz using TMS as an internal
standard. Data are reported as follows: chemical shift (δ ppm),
multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, m
= multiplet), integration, and coupling constants (J) in hertz
(Hz). HRMS were determined on a Q-Tof LS/MS System ESI
spectrometer.
Ru complex a. Orange solid (644.5 mg, 80% yield); mp: >300
1
°C; H NMR (400 MHz, DMSO) δ 8.71 (s, 2H), 8.52 (d, J =
7.6 Hz, 2H), 7.84–7.71 (m, 3H), 7.37 (d, J = 2.4 Hz, 2H),
7.28–7.98 (m, 15H), 6.87 (dd, J = 7.6, 2.8 Hz, 2H), 3.90 (s,
6H); 13C{1H} NMR (101 MHz, DMSO) δ 159.5, 153.8, 148.4,
145.2, 132.8, 132.7, 131.7, 131.3, 129.8, 129.3, 127.7, 118.9,
114.0, 108.9, 93.3, 55.8; 31P{1H} NMR (162 MHz, DMSO) δ
34.4 (s, PPh3); HRMS (ESI-TOF) m/z: [M + H]+ calcd for
C39H33Cl2N5O2PRu 806.0787, found 806.0724.
General Procedure for Preparation of ligand precursors
2a−c
In a 50 mL Schlenk flask was stirred 2,6-diacetylpyridine 1
(326.4 mg, 2.0 mmol) and p-toluenesulfoic acid monohydrate
(1.141 g, 6.0 mmol) in acetonitrile (10 mL). NBS (890 mg, 5.0
mmol) was added, and the solution was refluxed for 16 h. Af-
ter the reaction mixture was cooled to room temperature, the
solvent was evaporated to afford a crude product, which was
filtered by a short silica gel chromatography column with
CH2Cl2 as eluent to give α,α′-dibromo-2,6-diacetylpyridine
without further purification. The obtained intermediate com-
pound then reacted with 2-aminopyridine derivatives (5.0
mmol) and sodium hydrogen carbonate (504.1 mg, 6.0 mmol)
in acetonitrile (10 mL) at reflux for 7 h. After cooling and
filtration, the solvent was evaporated under vacuo. The residue
was purified via column chromatography using dichloro-
methane (DCM)/ethyl acetate (EA)/methanol (40/15/1) as
eluent to afford the corresponding product 2a−c.
Ru complex b. Orange solid (618.5 mg, 80% yield); mp: >300
1
°C; H NMR (400 MHz, DMSO) δ 8.77 (s, 2H), 8.54 (d, J =
7.2 Hz, 2H), 7.93–7.63 (m, 5H), 7.22–6.96 (m, 17H), 2.50 (s,
6H); 13C{1H} NMR (101 MHz, DMSO) δ 153.8, 147.0, 145.3,
139.7, 132.8, 132.7, 131.4, 131.0, 129.3, 128.4, 127.6, 127.5,
119.2, 116.7, 114.3, 114.1, 21.3; 31P{1H} NMR (162 MHz,
DMSO) δ 33.7 (s, PPh3); HRMS (ESI-TOF) m/z: [M + H]+
calcd for C39H33Cl2N5PRu 774.0889, found 774.0899.
Ru complex c. Red solid (722.9 mg, 82% yield); mp: >300
1
°C; H NMR (400 MHz, DMSO) δ 9.11 (s, 2H), 8.91 (d, J =
7.2 Hz, 2H), 8.36 (s, 2H), 8.08 (d, J = 8.0 Hz, 2H), 7.92 (t, J =
8.0 Hz, 2H), 7.51–7.39 (m, 2H), 7.28–6.96 (m, 17H); 13C{1H}
NMR (101 MHz, DMSO) δ 153.4, 147.2, 144.8, 132.5,
132.4,131.4, 131.0, 130.7, 129.6, 128.9, 128.2, 127.8, 127.7,
125.3, 121.5, 118.8 (q, JC-F = 349.7 Hz), 109.4; 19F NMR (376
MHz, DMSO) δ -62.77; 31P{1H} NMR (162 MHz, DMSO) δ
32.1 (s, PPh3); HRMS (ESI-TOF) m/z: [M − Cl]+ calcd for
C39H26ClF6N5PRu 846.0557, found 846.0556.
2,6-Bis(7-methoxyimidazo[1,2-a]pyridin-2-yl)pyridine (2a).
1
Yellow solid (248.8 mg, 67% yield); mp: 262−263 °C; H
NMR (400 MHz, CDCl3) δ 8.20 (s, 2H), 8.05 (d, J = 7.6 Hz,
2H), 7.97 (d, J = 7.6 Hz, 2H), 7.85 (t, J = 7.8 Hz, 1H), 6.93 (d,
J = 2.4 Hz, 2H), 6.54 (dd, J= 7.2, 2.4 Hz, 2H), 3.88 (s, 6H);
13C{1H} NMR (101 MHz, CDCl3) δ 158.0, 152.6, 147.1,
145.7, 137.5, 126.2, 119.0, 109.9, 108.0, 94.9, 55.5; HRMS
(ESI-TOF) m/z: [M + H]+ Calcd for C21H18N5O2 372.1445,
found 372.1455.
General Procedure for α-alkylation of ketones
To a 15 mL Schlenk tube was added ketone 3 or 7 (0.40
mmol), alcohols 4 (0.44 mmol), Ru complex b (1.6 mg, 0.5
mol%) and K3PO4·3H2O (16.0 mg, 0.15 equiv or 56.3 mg, 0.50
t
2,6-Bis(7-methylimidazo[1,2-a]pyridin-2-yl)pyridine (2b).
equiv) in amyl alcohol (0.5 mL) under an argon atmosphere.
1
o
Yellow solid (257.9 mg, 76% yield); mp: 258−260 °C; H
The reaction mixture was stirred at 120 C for 4–12 h. After
NMR (400 MHz, CDCl3) δ 8.27 (s, 2H), 8.05 (dd, J = 17.2, 7.6
Hz, 4H), 7.85 (t, J = 7.8 Hz, 1H), 7.39 (s, 2H), 6.67–6.57 (m,
2H), 2.39 (s, 6H); 13C{1H} NMR (101 MHz, CDCl3) δ 152.2,
the reaction was completed, the reaction mixture was evapo-
rated and the residue was purified by TLC on silica gel plates
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The Journal of Organic Chemistry
Page 6 of 13
using DCM/petroleum ether (PE) or EA/PE as eluent to afford
the corresponding ketone products 5 or 6 or 8.
3-(4-Iodophenyl)-1-phenylpropan-1-one (5h).8b Yellow sol-
1
2
3
4
5
6
7
8
id (104.9 mg, 78% yield); mp:71−73 °C; eluent DCM/PE (2/3);
1H NMR (400 MHz, CDCl3) δ 8.05–7.79 (m, 2H), 7.63–7.49
(m, 3H), 7.43 (t, J = 7.6 Hz, 2H), 6.99 (d, J = 8.4 Hz, 2H),
3.25 (t, J = 7.6 Hz, 2H), 2.99 (t, J = 7.4 Hz, 2H); 13C{1H}
NMR (101 MHz, CDCl3) δ 198.8, 141.0, 137.6 136.8, 133.2,
130.6, 128.7, 128.0, 91.3, 40.0, 29.6.
1,3-Diphenylpropan-1-one (5a).3c White solid (81.6 mg, 97%
1
yield); mp: 69−71 °C; eluent DCM/PE (2/3); H NMR (400
MHz, CDCl3) δ 7.96–7.94 (m, 2H), 7.57–7.53 (m, 1H), 7.44 (t,
J = 7.6 Hz, 2H), 7.32–7.18 (m, 5H), 3.32–3.28 (m, 2H), 3.07
(t, J = 7.6 Hz, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 199.3,
141.3, 136.9, 133.1, 128.6, 128.5, 128.4, 128.1, 126.2, 40.5,
30.1.
1-Phenyl-3-(4-(trifluoromethyl)phenyl)propan-1-one (5i).9
Yellow solid (74.6 mg, 67% yield); mp:45−46 °C; eluent
9
1
DCM/PE (1/3); H NMR (400 MHz, CDCl3) δ 7.96–7.93 (m,
3-(4-Methoxyphenyl)-1-phenylpropan-1-one (5b).4e Yellow
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
2H), 7.58–7.49 (m, 3H), 7.47–7.42 (m, 2H), 7.36 (d, J = 8.0
Hz, 2H), 3.34–3.29 (m, 2H), 3.13 (t, J = 7.4 Hz, 2H); 13C{1H}
NMR (101 MHz, CDCl3) δ 198.6, 145.5, 136.7, 133.3, 128.8,
128.7, 128.4, 123.3 (q, JC-F = 272.8 Hz), 125.4 (q, JC-F = 3.7
Hz), 39.8, 29.8; 19F NMR (376 MHz, CDCl3) δ -62.29.
1
oil (89.4 mg, 93% yield); eluent EA/PE (1/10); H NMR (400
MHz, CDCl3) δ 7.96–7.90 (m, 2H), 7.56–7.48 (m, 1H), 7.41 (t,
J = 7.6 Hz, 2H), 7.15 (d, J = 8.8 Hz, 2H), 6.82 (d, J = 8.4 Hz,
2H), 3.75 (s, 3H), 3.25–3.22 (m, 2H), 2.99 (t, J = 7.6 Hz, 2H);
13C{1H} NMR (101 MHz, CDCl3) δ 199.4, 158.1, 137.0,
133.4, 133.1, 129.4, 128.6, 128.1, 114.0, 55.3, 40.7, 29.3.
3-([1,1'-Biphenyl]-4-yl)-1-phenylpropan-1-one (5j).3c Yel-
low solid (108.7 mg, 95% yield); mp: 55−57 °C; eluent
4e
1-Phenyl-3-(p-tolyl)propan-1-one (5c).
Yellow oil (84.3
1
DCM/PE (2/3); H NMR (400 MHz, CDCl3) δ 7.97–7.89 (m,
1
mg, 94% yield); eluent DCM/PE (2/3); H NMR (400 MHz,
CDCl3) δ 7.97–7.89 (m, 2H), 7.55–7.48 (m, 1H), 7.41 (t, J =
7.6 Hz, 2H), 7.11 (q, J = 8.1 Hz, 4H), 3.26–3.22 (m, 2H), 3.01
(t, J = 7.8 Hz, 2H), 2.30 (s, 3H); 13C{1H} NMR (101 MHz,
CDCl3) δ 199.3, 138.3, 137.0, 135.6, 133.1 129.3, 128.7,
128.4, 128.1, 40.6, 29.8, 21.1.
2H), 7.59–7.46 (m, 5H), 7.42–7.36 (m, 4H), 7.31–7.26 (m,
3H), 3.28 (t, J = 7.6 Hz, 2H), 3.08 (t, J = 7.6 Hz, 2H); 13C{1H}
NMR (101 MHz, CDCl3) δ 199.2, 141.1, 140.5, 139.2, 136.9,
133.2, 129.0, 128.9, 128.7, 128.2, 127.3, 127.2, 127.1, 40.4,
29.8.
3-(3-Methoxyphenyl)-1-phenylpropan-1-one (5k).4e Brown
solid (93.2 mg, 97% yield); mp: 67−68 °C; eluent DCM/PE
(2/3); 1H NMR (400 MHz, CDCl3) δ 7.95–7.92 (m, 2H), 7.56–
7.48 (m, 1H), 7.45–7.40 (m, 2H), 7.20 (t, J = 8.0 Hz, 1H),
6.84–6.72 (m, 3H), 3.77 (s, 3H), 3.36–3.20 (m, 2H), 3.03 (t, J
= 7.6 Hz, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 199.2,
159.8, 143.0, 136.9, 133.1, 129.6, 128.6, 128.1, 120.8, 114.3,
111.5, 55.2, 40.4, 30.2.
1-Phenyl-3-(4-(trifluoromethoxy)phenyl)propan-1-one (5d).
4c
1
Red oil (100.1 mg, 85% yield); eluent DCM/PE (2/3); H
NMR (400 MHz, CDCl3) δ 7.99–7.93 (m, 2H), 7.57–7.51 (m,
1H), 7.43 (t, J = 7.6 Hz, 2H), 7.29–7.23 (m, 2H), 7.12 (d, J =
8.0 Hz, 2H), 3.28 (t, J = 7.4 Hz, 2H), 3.07 (t, J = 7.6 Hz, 2H);
13C{1H} NMR (101 MHz, CDCl3) δ 198.8, 147.6 (d, JC-F = 1.5
Hz), 140.1, 136.8, 133.2, 129.8, 128.6, 128.0, 121.1, 120.6 (q,
JC-F = 257.4 Hz), 40.1, 29.3; 19F NMR (376 MHz, CDCl3) δ -
57.91.
1-Phenyl-3-(m-tolyl)propan-1-one (5l).6 Yellow oil (79.0
1
mg, 88% yield); eluent DCM/PE (2/3); H NMR (400 MHz,
4e
3-(4-Fluorophenyl)-1-phenylpropan-1-one (5e).
White
CDCl3) δ 8.00–7.88 (m, 2H), 7.56–7.48 (m, 1H), 7.42 (t, J =
7.6 Hz, 2H), 7.20–7.15 (m, 1H), 7.08–6.97 (m, 3H), 3.29–3.24
(m, 2H), 3.01 (t, J = 7.6 Hz, 2H), 2.32 (s, 3H); 13C{1H} NMR
(101 MHz, CDCl3) δ 199.3, 141.3, 138.1, 136.9, 133.1, 129.3,
128.7, 128.5, 128.1, 127.0, 125.4, 40.6, 30.1, 21.5.
solid (79.4 mg, 87% yield); mp: 66−68 °C; eluent DCM/PE
(2/3); 1H NMR (400 MHz, CDCl3) δ 7.94–7.92 (m, 2H), 7.56–
7.49 (m, 1H), 7.43 (t, J = 7.6 Hz, 2H), 7.20–7.17 (m, 2H), 6.95
(t, J = 8.6 Hz, 2H), 3.25 (t, J = 7.4 Hz, 2H), 3.02 (t, J = 7.4 Hz,
2H); 13C{1H} NMR (101 MHz, CDCl3) δ 199.0, 161.4 (d, JC-F
= 244.6 Hz), 136.9 (d, JC-F = 3.1 Hz), 136.8, 133.1, 129.9 (d,
JC-F = 7.8 Hz), 128.7, 128.0, 115.3 (d, JC-F = 21.2 Hz), 40.4,
29.3; 19F NMR (376 MHz, CDCl3) δ -117.16.
3-(3-Fluorophenyl)-1-phenylpropan-1-one (5m).27 Yellow
solid (78.5 mg, 86% yield); mp:53−55 °C; eluent DCM/PE
(2/3); 1H NMR (400 MHz, CDCl3) δ 8.01–7.93 (m, 2H), 7.57–
7.51 (m, 1H), 7.44 (t, J = 7.6 Hz, 2H), 7.26–7.20 (m, 1H),
7.05–6.83 (m, 3H), 3.30–3.26 (m, 2H), 3.06 (t, J = 7.6 Hz,
3-(4-Chlorophenyl)-1-phenylpropan-1-one (5f).4e Yellow oil
1
(72.4 mg, 74% yield); eluent DCM/PE (2/3); H NMR (400
2H); 13C NMR (101 MHz, CDCl3) δ 198.8, 163.0 (d, JC-F
=
MHz, CDCl3 ) δ 8.00–7.88 (m, 2H), 7.58–7.51 (m, 1H), 7.48–
7.40 (m, 2H), 7.28–7.21 (m, 2H), 7.21–7.13 (m, 2H), 3.27 (t, J
= 7.6 Hz, 2H), 3.03 (t, J = 7.6 Hz, 2H); 13C{1H} NMR (101
MHz, CDCl3) δ 198.9, 139.8, 136.8, 133.2, 131.9, 129.9,
128.7, 128.6, 128.0, 40.1, 29.4.
246.5 Hz), 143.90 (d, JC-F = 7.2 Hz), 136.8, 133.2, 130.0 (d,
JC-F = 8.3 Hz), 128.7, 128.0, 124.1 (d, JC-F = 2.7 Hz), 115.3 (d,
JC-F = 20.9 Hz), 113.0 (d, JC-F = 21.2 Hz), 40.1, 29.8; 19F NMR
(376 MHz, CDCl3) δ -113.38.
1-Phenyl-3-(3-(trifluoromethyl)phenyl)propan-1-one (5n).4e
Yellow oil (57.9 mg, 52% yield); eluent DCM/PE (1/3); B1H
NMR (400 MHz, CDCl3 ) δ 8.01–7.94 (m, 2H), 7.61–7.33 (m,
7H), 3.34–3.30 (m, 2H), 3.13 (t, J = 7.4 Hz, 2H); 13C{1H}
NMR (101 MHz, CDCl3) δ 198.6, 142.2, 136.7, 133.2, 132.0,
4e
3-(4-Bromophenyl)-1-phenylpropan-1-one (5g).
Yellow
solid (91.4 mg, 79% yield); mp: 69−71 °C; eluent DCM/PE
(2/3); 1H NMR (400 MHz, CDCl3) δ 8.01–7.89 (m, 2H), 7.60–
7.52 (m, 1H), 7.50–7.37 (m, 4H), 7.13 (d, J = 8.4 Hz, 2H),
3.28 (t, J = 7.6 Hz, 2H), 3.03 (t, J = 7.6 Hz, 2H); 13C{1H}
NMR (101 MHz, CDCl3) δ 198.8, 140.3, 136.8, 133.2, 131.6,
130.2, 128.7, 128.0, 120.0, 40.1, 29.4.
130.8 (q, JC-F = 32.2 Hz), 129.0, 128.7, 128.0, 124.2 (q, JC-F
=
273.6 Hz), 125.2 (q, JC-F = 3.7 Hz), 123.1 (q, JC-F = 3.8 Hz),
40.0, 29.8; 19F NMR (376 MHz, CDCl3) δ -62.52.
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The Journal of Organic Chemistry
3-(2-Methoxyphenyl)-1-phenylpropan-1-one (5o).8b Yellow
oil (94.2 mg, 98% yield); eluent DCM/PE (2/3); 1H NMR (400
MHz, CDCl3 ) δ 8.06–7.86 (m, 2H), 7.55–7.48 (m, 1H), 7.44–
7.39 (m, 2H), 7.21–7.16 (m, 2H), 6.90–6.82 (m, 2H), 3.79 (s,
3H), 3.27–3.22 (m, 2H), 3.04 (t, J = 7.6 Hz, 2H); 13C{1H}
NMR (101 MHz, CDCl3) δ 200.0, 157.6, 137.0, 133.0, 130.2,
129.6, 128.6, 128.2, 127.6, 120.6, 110.3, 55.2, 39.0, 25.8.
3-(Furan-2-yl)-1-phenylpropan-1-one (5v).9 Brown solid
(31.2 mg, 39% yield); mp: 36−38 °C; eluent EA/PE (1/30); 1H
NMR (400 MHz, CDCl3) δ 8.02–7.94 (m, 2H), 7.60–7.53 (m,
1H), 7.46 (t, J = 7.6 Hz, 2H), 7.32–7.30 (m, 1H), 6.30–6.27
(m, 1H), 6.07–6.04 (m, 1H), 3.36–3.20 (m, 2H), 3.09 (t, J =
7.4 Hz, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 198.7, 154.8,
141.1, 136.8, 133.2, 128.6, 128.0, 110.3, 105.3, 36.9, 22.5.
1
2
3
4
5
6
7
8
3-(2-Fluorophenyl)-1-phenylpropan-1-one (5p).4e Yellow
oil (75.8 mg, 83% yield); eluent DCM/PE (2/3); 1H NMR (400
MHz, CDCl3) δ 7.96–7.93 (m, 2H), 7.57–7.50 (m, 1H), 7.43 (t,
J = 7.4 Hz, 2H), 7.28–7.23 (m, 1H), 7.21–7.14 (m, 1H), 7.09–
6.96 (m, 2H), 3.31–3.26 (m, 2H), 3.08 (t, J = 7.6 Hz, 2H);
1-Phenyl-3-(thiophen-2-yl)propan-1-one (5w).9 Yellow oil
9
1
(26.8 mg, 31% yield); eluent EA/PE (1/30); H NMR (400
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
MHz, CDCl3) δ 8.05–7.86 (m, 2H), 7.60–7.51 (m, 1H), 7.45 (t,
J = 7.6 Hz, 2H), 7.15–7.10 (m, 1H), 6.95–6.90 (m, 1H), 6.88–
6.81 (m, 1H), 3.38–3.28 (m, 4H); 13C{1H} NMR (101 MHz,
CDCl3) δ 198.6, 143.9, 136.8, 133.2, 128.7, 128.1, 126.9,
124.7, 123.4, 40.6, 24.2.
13C{1H} NMR (101 MHz, CDCl3) δ 199.0, 161.3 (d, JC-F
=
245.7 Hz), 136.8, 133.1, 130.9 (d, JC-F = 4.9 Hz), 128.6,
128.07 (d, JC-F = 15.8 Hz), 128.06, 128.0 (d, JC-F = 8.1 Hz),
124.1 (d, JC-F = 3.5 Hz), 115.3 (d, JC-F = 22.0 Hz), 38.9, 24.0;
19F NMR (376 MHz, CDCl3) δ -118.36.
1,5-Diphenylpentan-1-one (5x).7 Yellow oil (59.1 mg, 62%
1
yield); eluent DCM/PE (1/2) then PE; H NMR (400 MHz,
3-(2-Bromophenyl)-1-phenylpropan-1-one (5q).28 Yellow
oil (93.7 mg, 81% yield); eluent DCM/PE (2/3); 1H NMR (400
MHz, CDCl3) δ 7.97–7.94 (m, 2H), 7.57–7.48 (m, 2H), 7.45–
7.40 (m, 2H), 7.31–7.28 (m, 1H), 7.24–7.19 (m, 1H), 7.08–
7.03 (m, 1H), 3.33–3.24 (m, 2H), 3.19–3.15 (m, 2H); 13C{1H}
NMR (101 MHz, CDCl3) δ 198.9, 140.6, 136.8, 133.2, 132.9,
130.8, 128.7, 128.1, 128.0, 127.7, 124.4, 38.6, 30.8.
CDCl3) δ 7.99–7.87 (m, 2H), 7.55–7.49 (m, 1H), 7.43 (t, J =
7.6 Hz, 2H), 7.30–7.22 (m, 2H), 7.19–7.14 (m, 3H), 2.96 (t, J
= 7.0 Hz, 2H), 2.65 (t, J = 7.6 Hz, 2H), 1.83–1.65 (m, 4H);
13C{1H} NMR (101 MHz, CDCl3) δ 200.3, 142.3, 137.1,
133.0, 128.6, 128.5, 128.4, 128.1, 125.8, 38.4, 35.9, 31.1,
24.0.
1-Phenylhexan-1-one (5y).30 Yellow oil (47.2 mg, 67%
1
1-Phenyl-3-(2-(trifluoromethyl)phenyl)propan-1-one (5r).29
yield); eluent DCM/PE (1/4); H NMR (400 MHz, CDCl3) δ
Yellow solid (108.0 mg, 97% yield); mp: 60−62 °C; eluent
8.01–7.94 (m, 2H), 7.57–7.51 (m, 1H), 7.49–7.41 (m, 2H),
2.96 (t, J = 7.4 Hz, 2H), 1.86–1.68 (m, 2H), 1.40–1.34 (m,
4H), 0.91 (t, J = 7.0 Hz, 3H); 13C{1H} NMR (101 MHz,
CDCl3) δ 200.6, 137.1, 132.8, 128.5, 128.0, 38.6, 31.6, 24.1,
22.5, 14.0.
1
DCM/PE (2/3); H NMR (400 MHz, CDCl3 ) δ 7.96–7.93 (m,
2H), 7.63 (d, J = 8 Hz, 1H), 7.58–7.50 (m, 1H), 7.50–7.35 (m,
4H), 7.30 (t, J = 7.6 Hz, 1H), 3.38–3.14 (m, 4H); 13C{1H}
NMR (101 MHz, CDCl3) δ 198.6, 140.2, 136.7, 133.2, 132.0,
131.4, 128.7, 128.6 (q, JC-F = 29.7 Hz), 128.0, 126.4, 126.1 (q,
JC-F = 5.8 Hz), 123.3, 40.5, 27.1; 19F NMR (376 MHz, CDCl3)
δ -59.63.
1-Phenyloctan-1-one (5z).3c Yellow oil (41.7 mg, 51% yield);
1
eluent DCM/PE (1/3); H NMR (400 MHz, CDCl3) δ 8.00–
7.92 (m, 2H), 7.59–7.50 (m, 1H), 7.50–7.41 (m, 2H), 2.96 (t, J
= 7.4 Hz, 2H), 1.80–1.69 (m, 2H), 1.41–1.25 (m, 9H), 0.88 (t,
J = 6.8 Hz, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ 200.6,
137.1, 132.8, 128.5, 128.1, 38.6, 31.7, 29.4, 29.2, 24.4, 22.6,
14.1.
3-(3,4-Dimethoxyphenyl)-1-phenylpropan-1-one
(5s).4c
Yellow solid (90.8 mg, 84% yield); mp: 71−73 °C; eluent
1
DCM/PE (2/3); H NMR (400 MHz, CDCl3) δ 7.99–7.93 (m,
2H), 7.59–7.52 (m, 1H), 7.45 (t, J = 7.6 Hz, 2H), 6.80–6.78
(m, 3H), 3.86 (d, J = 4.8 Hz, 6H), 3.31–3.27 (m, 2H), 3.02 (t, J
= 7.6 Hz, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 199.3,
148.9, 147.4, 136.9, 133.9, 133.1, 128.6, 128.0, 120.2, 111.9,
111.4, 55.9, 55.8, 40.6, 29.8.
3-Cyclohexyl-1-phenylpropan-1-one (5aa).9 Yellow oil (71.8
1
mg, 83% yield); eluent DCM/PE (1/3); H NMR (400 MHz,
CDCl3) δ 7.99–7.91 (m, 2H), 7.58–7.48 (m, 1H), 7.44 (t, J =
7.6 Hz, 2H), 2.97 (t, J = 7.8 Hz, 2H), 1.82–1.56 (m, 7H), 1.39–
1.07 (m, 4H), 1.02 – 0.85 (m, 2H); 13C{1H} NMR (101 MHz,
CDCl3) δ 200.8, 137.1, 132.8, 128.5, 128.1, 37.4, 36.2, 33.2,
31.8, 26.6, 26.3.
3-(2,4-Dichlorophenyl)-1-phenylpropan-1-one (5t).4c Yel-
low oil (96.0 mg, 86% yield); eluent DCM/PE (2/3) then
DCM/PE (1/10); 1H NMR (400 MHz, CDCl3) δ 7.98–7.91 (m,
2H), 7.58–7.51 (m, 1H), 7.44 (t, J = 7.6 Hz, 2H), 7.35 (d, J =
2.4 Hz, 1H), 7.24 (d, J = 8.4 Hz, 1H), 7.17–7.14 (m, 1H),
3.35–3.22 (m, 2H), 3.13 (t, J = 7.4 Hz, 2H); 13C{1H} NMR
(101 MHz, CDCl3) δ 198.6, 137.5, 136.6, 134.6, 133.2, 132.7,
131.7, 129.3, 128.7, 128.0, 127.2, 38.1, 27.7.
4-Methyl-1-phenylpentan-1-one
(5ab).31
Yellow
oil
1
(56.4mg, 80% yield); eluent DCM/PE (1/4); H NMR (400
MHz, CDCl3) δ 8.00–7.92(m, 2H), 7.59–7.50 (m, 1H), 7.49–
7.41 (m, 2H), 2.90 (t, J = 7.4 Hz, 2H), 1.77–1.50 (m, 3H), 0.95
(d, J = 6.4 Hz, 6H); 13C{1H} NMR (101 MHz, CDCl3) δ
200.7, 137.1, 132.9, 128.6, 128.1, 36.6, 33.3, 27.9, 22.4.
1-Phenyl-3-(pyridin-3-yl)propan-1-one (5u).9 Yellow solid
1
(19.4 mg, 23% yield); mp: 82−85 °C; eluent EA/PE (1/4); H
4-Methyl-1-phenylhexan-1-one (5ac).4e Yellow oil (45.7mg,
60% yield); eluent DCM/PE (1/4); 1H NMR (400 MHz,
CDCl3) δ 8.00–7.93 (m, 2H), 7.59–7.51 (m, 1H), 7.50–7.41
(m, 2H), 3.05–2.88 (m, 2H), 1.83–1.73 (m, 1H), 1.60–1.50 (m,
1H), 1.46–1.34 (m, 2H), 1.28–1.16 (m, 2H), 0.96–0.86 (m,
6H); 13C{1H} NMR (101 MHz, CDCl3) δ 200.9, 137.1, 132.9,
128.6, 128.1, 36.4, 34.2, 31.0, 29.3, 19.1, 11.4.
NMR (400 MHz, CDCl3) δ 8.57–8.52 (m, 1H), 8.48–8.43 (m,
1H), 7.98–7,92 (m, 2H), 7.63–7.52 (m, 2H), 7.46 (t, J = 7.6
Hz, 2H), 7.24–7.20 (m, 1H), 3.32 (t, J = 7.4 Hz, 2H), 3.09 (t, J
= 7.6 Hz, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 198.5,
149.9, 147.6, 136.6, 136.1, 133.3, 128.7, 128.0, 123.4, 39.7,
27.1.
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(m, 1H), 7.91–7.78 (m, 3H), 7.57–7.47 (m, 2H), 7.33–7.15 (m,
1,3-Diphenylbutan-1-one (5ad).32 Yellow solid (49.3 mg,
55% yield); mp: 74−76 °C; eluent DCM/PE (1/2) then PE; H
5H), 3.41–3.36 (m, 2H), 3.10 (t, J = 7.8 Hz, 2H); 13C{1H}
NMR (101 MHz, CDCl3) δ 199.2, 141.4, 135.6, 134.2, 132.6,
129.7, 129.6, 128.64, 128.56, 128.5, 127.8, 126.8, 126.2,
123.9, 40.6, 30.3.
1
2
3
4
5
6
7
8
1
NMR (400 MHz, CDCl3) δ 7.97–7.84 (m, 2H), 7.55–7.48 (m,
1H), 7.41 (t, J = 7.6 Hz, 2H), 7.32–7.23 (m, 4H), 7.23–7.14
(m, 1H), 3.54–3.47 (m, 1H), 3.33–3.25 (m, 1H), 3.20–3.13 (m,
1H), 1.33 (d, J = 6.8 Hz, 3H); 13C{1H} NMR (101 MHz,
CDCl3) δ 199.1, 146.6, 137.3, 133.0, 128.61, 128.58, 128.1,
126.9, 126.3, 47.1, 35.6, 21.9.
3-Phenyl-1-(thiophen-2-yl)propan-1-one (6h).9 Yellow Oil
1
(17.3 mg, 20% yield); eluent DCM/PE (1/4) then PE; H NMR
(400 MHz, CDCl3) δ 7.70–7.67 (m, 1H), 7.64–7.60 (m, 1H),
7.33–7.17 (m, 5H), 7.12–7.09 (m, 1H), 3.27–3.19 (m, 2H),
3.07 (t, J = 7.6 Hz, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ
192.2, 144.2, 141.0, 133.6, 131.8, 128.6, 128.4, 128.1, 126.2,
41.2, 30.4.
1-(4-Methoxyphenyl)-3-phenylpropan-1-one (6a).7 Yellow
solid (93.2 mg, 97% yield); mp: 97−98 °C; eluent DCM/PE
(2/3); 1H NMR (400 MHz, CDCl3) δ 7.92 (d, J = 8.8 Hz, 2H),
7.34–7.13 (m, 5H), 6.90 (d, J = 9.2 Hz, 2H), 3.83 (s, 3H),
3.26–3.19 (m, 2H), 3.04 (t, J = 7.6 Hz, 2H); 13C{1H} NMR
(101 MHz, CDCl3) δ 197.8, 163.5, 141.5, 130.3, 130.0, 128.54,
128.46, 126.1, 113.8, 55.5, 40.1, 30.4.
9
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-(1-Methyl-1H-pyrrol-2-yl)-3-phenylpropan-1-one (6i).30
1
Brown oil (76.8 mg, 90% yield); eluent DCM/PE (2/3); H
NMR (400 MHz, CDCl3) δ 7.32–7.11 (m, 5H), 6.94–6.90 (m,
1H), 6.77–6.74 (m, 1H), 6.10–6.07 (m, 1H), 3.91 (s, 3H),
3.15–2.94 (m, 4H); 13C{1H} NMR (101 MHz, CDCl3) δ 190.2,
141.6, 131.0, 130.6, 128.52, 128.46, 126.1, 119.1, 108.0, 40.8,
37.7, 30.9.
3-Phenyl-1-(p-tolyl)propan-1-one (6b).4e Yellow oil (88.8
1
mg, 99% yield); eluent DCM/PE (2/3); H NMR (400 MHz,
CDCl3) δ 7.83 (d, J = 8.4 Hz, 2H), 7.31–7.11 (m, 7H), 3.28–
3.21 (m, 2H), 3.03 (t, J = 7.8 Hz, 2H), 2.37 (s, 3H); 13C{1H}
NMR (101 MHz, CDCl3) δ 198.9, 143.8, 141.4, 134.4, 129.3,
128.54, 128.46, 128.2, 126.1, 40.4, 30.3, 21.7.
1-Phenyloctan-3-one (6j).8b Yellow oil (33.5 mg, 41% yield);
1
eluent DCM/PE (1/4) then PE; H NMR (400 MHz, CDCl3) δ
7.33–7.12 (m, 5H), 2.89 (t, J = 7.6 Hz, 2H), 2.72 (t, J = 7.6
Hz, 2H), 2.37 (t, J = 7.4 Hz, 2H), 1.61–1.51 (m, 2H), 1.35–
1.17 (m, 4H), 0.87 (t, J = 7.2 Hz, 3H); 13C{1H} NMR (101
MHz, CDCl3) δ 210.4, 141.2, 128.5, 128.3, 126.1, 44.2, 43.0,
31.4, 29.8, 23.5, 22.4, 13.9.
1-(4-Fluorophenyl)-3-phenylpropan-1-one (6c).4e Yellow oil
1
(59.3 mg, 65% yield); eluent DCM/PE (2/3); H NMR (400
MHz, CDCl3) δ 8.00–7.91 (m, 2H), 7.31–7.17 (m, 5H), 7.13–
7.05 (m, 2H), 3.30–3.20 (m, 2H), 3.05 (t, J = 7.6 Hz, 2H);
13C{1H} NMR (101 MHz, CDCl3) δ 197.6, 165.7 (d, JC-F
=
255.6 Hz), 141.2, 133.3 (d, JC-F = 2.9 Hz), 130.7, 128.6, 128.4,
126.2, 115.7 (d, JC-F = 21.9 Hz), 40.4, 30.1; 19F NMR (376
MHz, CDCl3) δ -105.28.
5-Methyl-1-phenylhexan-3-one (6k).31 Yellow oil (50.2 mg,
66% yield); eluent EA/PE (1/80) then PE; 1H NMR (400 MHz,
CDCl3) δ 7.31−7.23 (m, 2H), 7.21−7.15 (m, 3H), 2.89 (t, J =
7.6 Hz, 2H), 2.70 (t, J = 7.6 Hz, 2H), 2.26 (d, J = 6.8 Hz, 2H),
2.18−2.05 (m, 1H), 0.89 (d, J = 6.6 Hz, 6H); 13C{1H} NMR
(101 MHz, CDCl3) δ 209.9, 141.2, 128.5, 128.3, 126.1, 52.1,
44.8, 29.7, 24.6, 22.6.
1-(4-Chlorophenyl)-3-phenylpropan-1-one (6d).4e Yellow
solid (72.4 mg, 74% yield); mp: 76−78 °C; eluent DCM/PE
(2/3); 1H NMR (400 MHz, CDCl3) δ 7.87 (d, J = 8.4 Hz, 2H),
7.40 (d, J = 8.8 Hz, 2H), 7.33–7.15 (m, 5H), 3.28–3.23 (m,
2H), 3.05 (t, J = 7.8 Hz, 2H); 13C{1H} NMR (101 MHz,
CDCl3) δ 198.0, 141.1, 139.5, 135.2, 129.5, 128.9, 128.6,
128.4, 126.2, 40.4, 30.1.
4,4-Dimethyl-1-phenylpentan-3-one (6l).4e Yellow solid
(15.2 mg, 20% yield); mp: 44−46 °C; eluent EA/PE (1/80)
1
then PE; H NMR (400 MHz, CDCl3) δ 7.36–7.13 (m, 5H),
2.95–2.69 (m, 4H), 1.10 (s, 9H); 13C NMR (101 MHz, CDCl3)
1-(3-Methoxyphenyl)-3-phenylpropan-1-one (6e).8b Yellow
oil (79.8 mg, 83% yield); eluent DCM/PE (2/3); 1H NMR (400
MHz, CDCl3) δ 7.55–7.45 (m, 2H), 7.36–7.15 (m, 6H), 7.10–
7.06 (m, 1H), 3.81 (s, 3H), 3.29–3.24 (m, 2H), 3.05 (t, J = 7.6
Hz, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 199.0, 159.9,
141.3, 138.3, 129.6, 128.6, 128.5, 126.2, 120.7, 119.6, 112.3,
55.5, 40.6, 30.2.
δ 215.0, 141.6, 128.44, 128.40, 126.0, 44.1, 38.5, 30.1, 26.3.
1,2,3-Triphenylpropan-1-one (8a).19 White solid (103.0 mg,
90% yield); mp: 122−124 °C; eluent DCM/PE (2/3); 1H NMR
(400 MHz, CDCl3) δ 7.89 (d, J = 7.6 Hz, 2H), 7.44–7.38 (m,
1H), 7.31 (t, J = 7.6 Hz, 2H), 7.27–7.05 (m, 10H), 4.81 (t, J =
7.2 Hz, 1H), 3.60–3.53 (m, 1H), 3.10–3.03 (m, 1H); 13C{1H}
NMR (101 MHz, CDCl3) δ 199.3, 139.8, 139.2, 136.8, 132.9,
129.2, 129.0, 128.7, 128.5, 128.4, 128.3, 127.2, 126.2, 56.0,
40.2.
1-(Naphthalen-1-yl)-3-phenylpropan-1-one (6f).31 Yellow
oil (83.3 mg, 80% yield); eluent DCM/PE (2/3); 1H NMR (400
MHz, CDCl3) δ 8.55 (d, J = 8.8 Hz, 1H), 7.91 (d, J = 8.4 Hz,
1H), 7.82 (d, J = 7.6 Hz, 1H), 7.78–7.74 (m, 1H), 7.58–7.45
(m, 2H), 7.43–7.38 (m, 1H), 7.31–7.15 (m, 5H), 3.33 (t, J =
7.6 Hz, 2H), 3.11 (t, J = 7.6 Hz, 2H); 13C{1H} NMR (101
MHz, CDCl3) δ 203.6, 141.2, 136.0, 134.0, 132.6, 130.2,
128.6, 128.55, 128.49, 128.0, 127.5, 126.5, 126.2, 125.9,
124.4, 43.8, 30.7.
3-(4-Methoxyphenyl)-1,2-diphenylpropan-1-one (8b). Yel-
low solid (117.7 mg, 93% yield); mp: 103−104 °C; eluent
1
DCM/PE (2/3); H NMR (400 MHz, CDCl3) δ 7.94–7.82 (m,
2H), 7.46–7.36 (m, 1H), 7.31 (t, J = 7.6 Hz, 2H), 7.27–7.13
(m, 5H), 6.99 (d, J = 8.4 Hz, 2H), 6.72 (d, J = 8.8 Hz, 2H),
4.77 (t, J = 7.4 Hz, 1H), 3.70 (s, 3H), 3.53–3.47 (m, 1H),
3.04–2.98 (m, 1H); 13C{1H} NMR (101 MHz, CDCl3) δ 199.5,
158.0, 139.2, 136.9, 132.9, 131.9, 130.1, 128.9, 128.7, 128.5,
128.4, 127.2, 113.7, 56.2, 55.2, 39.3. IR (KBr pellet): ν 2954,
1671 (νc=o), 1597, 1512, 1445, 1239, 1185, 818, 753, 691 cm−1;
1-(Naphthalen-2-yl)-3-phenylpropan-1-one (6g).9 Yellow
solid (100.0 mg, 96% yield); mp: 94−95 °C; eluent DCM/PE
1
(2/3); H NMR (400 MHz, CDCl3) δ 8.41 (s, 1H), 8.02–7.98
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The Journal of Organic Chemistry
HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C22H20NaO2
339.1356, found 339.1350.
(KBr pellet): ν 2922, 1679 (νc=o), 1597, 1494, 1448, 1329,
1161, 1119, 1073, 758, 697 cm−1; HRMS (ESI-TOF) m/z: [M
1
2
+ H]+ calcd for C22H18F3O 355.1304, found 355.1308.
1,2-Diphenyl-3-(4-(trifluoromethoxy)phenyl)propan-1-one
(8c). White solid (106.7 mg, 72% yield); mp: 74−75 °C; eluent
DCM/PE (2/3) then DCM/PE (1/4); 1H NMR (400 MHz,
CDCl3) δ 7.95–7.84 (m, 2H), 7.46–7.38 (m, 1H), 7.32 (t, J =
7.6 Hz, 2H), 7.28–7.15 (m, 5H), 7.08 (d, J = 8.8 Hz, 4H), 7.02
(d, J = 8.4 Hz, 4H), 4.77 (t, J = 7.4 Hz, 1H), 3.58–3.52 (m,
1H), 3.09–3.03 (m, 1H); 13C{1H} NMR (101 MHz, CDCl3) δ
198.9, 147.7, 138.8, 138.6, 136.6, 133.0, 130.5, 129.1, 128.7,
128.6, 128.3, 127.4, 120.5 (q, JC-F = 257.8 Hz), 120.8, 55.9,
39.4; 19F NMR (376 MHz, CDCl3) δ -57.83; IR (KBr pellet): ν
2922, 1679 (νc=o), 1509, 1214, 1157, 825, 754, 697 cm−1;
HRMS (ESI-TOF) m/z: [M + H]+ calcd for C22H18F3O2
371.1253, found 371.1263.
3
4
5
6
7
8
9
3-(2-Fluorophenyl)-1,2-diphenylpropan-1-one (8h). Yellow
solid (73.0 mg, 60% yield); mp: 113−114 °C; eluent DCM/PE
(1/5); 1H NMR (400 MHz, CDCl3) δ 7.90 (d, J = 7.6 Hz, 2H),
7.48–7.39 (m, 1H), 7.33 (t, J = 7.6 Hz, 2H), 7.27–7.07 (m,
6H), 7.03–6.86 (m, 3H), 4.90 (t, J = 7.4 Hz, 1H), 3.57–3.51
(m, 1H), 3.16–3.10 (m, 1H); 13C{1H} NMR (101 MHz,
CDCl3) δ 199.0, 161.4 (d, JC-F = 245.8 Hz), 138.9, 136.6,
132.9, 132.0 (d, JC-F = 4.9 Hz), 128.9, 128.7, 128.5, 128.2,
128.0 (d, JC-F = 8.3 Hz), 127.2, 126.5 (d, JC-F = 15.5 Hz), 123.8
(d, JC-F = 3.5 Hz), 115.1 (d, JC-F = 22.0 Hz), 54.0, 33.8; 19F
NMR (376 MHz, CDCl3) δ -118.17; IR (KBr pellet): ν 2964,
1675 (νc=o), 1581, 1489, 1448, 1209, 1100, 953, 756, 697 cm−1;
HRMS (ESI-TOF) m/z: [M + H]+ calcd for C21H18FO
305.1336, found 305.1341.
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
3-([1,1'-Biphenyl]-4-yl)-1,2-diphenylpropan-1-one
(8d).
White solid (102.9 mg, 71% yield); mp: 160−162 °C; eluent
DCM/PE (2/3) then DCM/PE (1/4); 1H NMR (400 MHz,
CDCl3) δ 7.97–7.86 (m, 2H), 7.53 (d, J = 7.2 Hz, 2H), 7.47–
7.18 (m, 13H), 7.15 (d, J = 8.0 Hz, 2H), 4.85 (t, J = 7.2 Hz,
1H), 3.64–3.58 (m, 1H), 3.13–3.07 (m, 1H); 13C{1H} NMR
(101 MHz, CDCl3) δ 199.2, 140.9, 139.1, 138.99, 138.95,
136.8, 132.9, 129.6, 129.0, 128.73, 128.71, 128.5, 128.3,
127.2, 127.1, 127.0, 55.9, 39.8; IR (KBr pellet): ν 3030, 1676
(νc=o), 1597, 1484, 1448, 1244, 956, 827, 761, 693 cm−1;
HRMS (ESI-TOF) m/z: [M + H]+ calcd for C27H23O 363.1743,
found 363.1749.
3-(2-Bromophenyl)-1,2-diphenylpropan-1-one (8i). Yellow
1
oil (118.3 mg, 81% yield); eluent DCM/PE (1/5); H NMR
(400 MHz, CDCl3) δ 7.90 (d, J = 7.6 Hz, 2H), 7.53–7.47 (m,
1H), 7.44–7.37 (m, 1H), 7.31 (t, J = 7.6 Hz, 2H), 7.28–7.14
(m, 5H), 7.08–6.94 (m, 3H), 5.05 (t, J = 7.2 Hz, 1H), 3.70–
3.63 (m, 1H), 3.20–3.14 (m, 1H); 13C{1H} NMR (101 MHz,
CDCl3) δ 199.0, 139.0, 138.9, 136.7, 132.9, 132.7, 132.2,
129.0, 128.7, 128.5, 128.3, 128.1, 127.3, 127.2, 124.7, 53.2,
40.4; IR (KBr pellet): ν 3067, 1678 (νc=o), 1597, 1494, 1469,
1207, 1023, 745, 695, 553 cm−1; HRMS (ESI-TOF) m/z: [M +
H]+ calcd for C21H18BrO 365.0536, found 365.0547.
3-(4-Chlorophenyl)-1,2-diphenylpropan-1-one (8e). White
solid (89.8 mg, 70% yield); mp: 120−121 °C; eluent DCM/PE
1,2-Diphenyl-3-(pyridin-3-yl)propan-1-one (8j). Yellow
1
(2/3) then DCM/PE (1/4); H NMR (400 MHz, CDCl3) δ 7.89
solid (60.9 mg, 53% yield); mp: 152−153 °C; eluent EA/PE
1
(d, J = 7.2 Hz, 2H), 7.42 (t, J = 7.4 Hz, 1H), 7.32 (t, J = 7.6
Hz, 2H), 7.28–7.10 (m, 7H), 6.99 (d, J = 8.4 Hz, 2H), 4.75 (t,
J = 7.4 Hz, 1H), 3.54–3.47 (m, 1H), 3.06–3.00 (m, 1H);
13C{1H} NMR (101 MHz, CDCl3) δ 198.9, 138.8, 138.3,
136.6, 133.0, 132.0, 130.6, 129.0, 128.7, 128.6, 128.4, 128.3,
127.3, 55.9, 39.5; IR (KBr pellet): ν 2922, 1669 (νc=o), 1595,
1492, 1448, 1264, 1210, 813, 753, 700, 686 cm−1; HRMS
(ESI-TOF) m/z: [M + H]+ calcd for C21H18ClO 321.1041,
found 321.1051.
(1/5); H NMR (400 MHz, CDCl3) δ 8.43–8.32 (m, 2H), 7.90
(d, J = 7.2 Hz, 2H), 7.43 (t, J = 7.4 Hz, 1H), 7.35–7.31 (m,
3H), 7.29–7.16 (m, 5H), 7.10–7.06 (m, 1H), 4.77 (t, J = 7.2
Hz, 1H), 3.55–3.49 (m, 1H), 3.11–3.05 (m, 1H); 13C{1H}
NMR (101 MHz, CDCl3) δ 198.6, 150.5, 147.7, 138.4, 136.8,
136.4, 135.2, 133.1, 129.1, 128.7, 128.6, 128.3, 127.5, 123.1,
55.7, 37.2. IR (KBr pellet): ν 2927, 1673 (νc=o), 1594, 1491,
1439, 1246, 1027, 961, 756, 697, 544 cm−1; HRMS (ESI-TOF)
m/z: [M + H]+ calcd for C20H18NO 288.1383, found 288.1389.
3-(3-Methoxyphenyl)-1,2-diphenylpropan-1-one (8f).33 Yel-
low oil (107.6 mg, 85% yield); eluent DCM/PE (2/3) then
DCM/PE (1/4); 1H NMR (400 MHz, CDCl3 ) δ 7.90 (d, J = 7.2
Hz, 2H), 7.44–7.37 (m, 1H), 7.31 (t, J = 7.6 Hz, 2H), 7.27–
7.14 (m, 5H), 7.09 (t, J = 7.8 Hz, 1H), 6.72–6.63 (m, 2H),
6.61–6.58 (m, 1H), 4.81 (t, J = 7.2 Hz, 1H), 3.65 (s, 3H),
3.57–3.51 (m, 1H), 3.08–3.02 (m, 1H); 13C{1H} NMR (101
MHz, CDCl3) δ 199.3, 159.5, 141.4, 139.2, 136.8, 132.9,
129.2, 129.0, 128.7, 128.5, 128.4, 127.2, 121.5, 114.8, 111.8,
55.8, 55.1, 40.2.
3-(Furan-2-yl)-1,2-diphenylpropan-1-one (8k).19 Brown
solid (80.2 mg,70% yield); mp: 55−59 °C; eluent DCM/PE
(2/3); 1H NMR (400 MHz, CDCl3) δ 7.97–7.90 (m, 2H), 7.48–
7.40 (m, 1H), 7.34 (t, J = 7.6 Hz, 2H), 7.29–7.14 (m, 6H),
6.19−6.16 (m, 1H), 5.88−5.86 (m, 1H), 5.01–4.97 (m, 1H),
3.61−3.55 (m, 1H), 3.13−3.06 (m, 1H); 13C{1H} NMR (101
MHz, CDCl3) δ 198.8, 153.4, 141.1, 138.8, 136.5, 133.0,
129.0, 128.8, 128.6, 128.1, 127.3, 110.3, 106.6, 52.6, 32.5.
1,2,5-Triphenylpentan-1-one (8l).34 Yellowish oil (81.8 mg,
65% yield); eluent DCM/PE (1/3); 1H NMR (400 MHz,
CDCl3) δ 7.92 (d, J = 7.2 Hz, 2H), 7.46–7.39 (m, 1H), 7.37–
7.30 (m, 2H), 7.30–7.19 (m, 6H), 7.19–7.09 (m, 4H), 4.53 (t, J
= 7.4 Hz, 1H), 2.74–2.49 (m, 2H), 2.35–2.15 (m, 1H), 1.99–
1.79 (m, 1H), 1.74–1.46 (m, 2H); 13C{1H} NMR (101 MHz,
CDCl3) δ 200.0 (s), 142.3, 139.7, 137.0, 132.9, 129.0, 128.7,
128.6, 128.5, 128.4, 128.3, 127.1, 125.8, 53.6, 36.0, 33.8,
29.6.
1,2-Diphenyl-3-(3-(trifluoromethyl)phenyl)propan-1-one
(8g). Yellow oil (119.9 mg, 78% yield); eluent DCM/PE (1/3);
1H NMR (400 MHz, CDCl3) δ 7.92–7.86 (m, 2H), 7.45–7.35
(m, 2H), 7.35–7.15 (m, 10H), 4.77 (t, J = 7.4 Hz, 1H), 3.61–
3.55 (m, 1H), 3.16–3.10 (m, 1H); 13C{1H} NMR (101 MHz,
CDCl3) δ 198.7, 140.7, 138.6, 136.5, 133.0, 132.7, 130.5 (q, J
= 32.0 Hz), 129.1, 128.7, 128.64, 128.57, 128.3, 127.4, 125.9
(q, JC-F = 3.7 Hz), 124.5 (q, JC-F = 400.6 Hz), 123.1 (q, JC-F
=
3.7 Hz), 55.8, 39.9; 19F NMR (376 MHz, CDCl3) δ -62.51; IR
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3-cyclohexyl-1,2-diphenylpropan-1-one (8m).35 White solid
Page 10 of 13
7.13 (m, 7H), 3.50–3.45 (m, 1H), 2.96–2.82 (m, 2H), 2.76–
2.59 (m, 2H), 2.12–2.04 (m, 1H), 1.81–1.70 (m, 1H); 13C{1H}
NMR (101 MHz, CDCl3) δ 199.4, 144.1, 140.1, 133.3, 132.5,
129.3, 128.8, 128.5, 127.6, 126.7, 126.2, 49.5, 35.7, 28.7,
27.7.
1
2
3
4
5
6
7
8
(74.8 mg, 64% yield); mp: 74−76 °C; eluent DCM/PE (1/3);
1H NMR (400 MHz, CDCl3) δ 7.97 (d, J = 7.6 Hz, 2H), 7.48–
7.42 (m, 1H), 7.40–7.34 (m, 2H), 7.33–7.24 (m, 4H), 7.21–
7.14 (m, 1H), 4.72 (t, J = 7.2 Hz, 1H), 2.21–2.06 (m, 1H),
1.84–1.55 (m, 6H), 1.23–1.08 (m, 4H), 1.02–0.85 (m, 2H);
13C{1H} NMR (101 MHz, CDCl3) δ 200.1, 140.1, 137.0,
132.8, 128.9, 128.7, 128.6, 128.3, 126.9, 50.6, 41.8, 35.4,
33.6, 33.3, 26.6, 26.20, 26.18.
2-(4-Methoxybenzyl)-3,4-dihydronaphthalen-1(2H)-one
(8t).12b Red solid (96.9 mg, 91% yield); mp: 90−91 °C; eluent
DCM/PE (2/3); H NMR (400 MHz, CDCl3) δ 8.08–8.03 (m,
1
1H), 7.48–7.39 (m, 1H), 7.29 (t, J = 7.6 Hz, 1H), 7.20 (d, J =
7.6 Hz, 1H), 7.14 (d, J = 8.8 Hz, 2H), 6.87–6.80 (m, 2H), 3.77
(s, 3H), 3.43–3.35 (m, 1H), 3.00–2.84 (m, 2H), 2.75–2.56 (m,
2H), 2.18–2.02 (m, 1H), 1.87–1.64 (m, 1H); 13C{1H} NMR
(101 MHz, CDCl3) δ 199.6, 158.0, 144.1, 133.3, 132.5, 132.0,
130.2, 128.7, 127.5, 126.6, 113.8, 55.3, 49.6, 34.8, 28.6, 27.6.
1,2-Diphenyloctan-1-one (8n).36 Yellow oil (70.7 mg, 63%
yield); eluent DCM/PE (1/3); H NMR (400 MHz, CDCl3) δ
9
1
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
7.96 (d, J = 7.2 Hz, 2H), 7.49–7.41 (m, 1H), 7.36 (t, J = 7.6
Hz, 2H), 7.33–7.22 (m, 4H), 7.21–7.14 (m, 1H), 4.54 (t, J =
7.4 Hz, 1H), 2.23–2.13 (m, 1H), 1.87–1.77 (m, 1H), 1.35–1.18
(m, 8H), 0.84 (t, J = 7.0 Hz, 3H); 13C{1H} NMR (101 MHz,
CDCl3) δ 200.2, 140.0, 137.1, 132.8, 128.9, 128.7, 128.5,
128.3, 126.9, 53.7, 34.1, 31.7, 29.3, 27.7, 22.6, 14.1.
2-(4-Methylbenzyl)-3,4-dihydronaphthalen-1(2H)-one
(8u).3c Brown oil (92.0 mg, 92% yield); eluent DCM/PE (2/3);
1H NMR (400 MHz, CDCl3) δ 8.01–7.94 (m, 1H), 7.38–7.32
(m, 1H), 7.19 (t, J = 7.6 Hz, 1H), 7.10 (d, J = 7.6 Hz, 1H),
7.01 (s, 4H), 3.37–3.31 (m, 1H), 2.88–2.74 (m, 2H), 2.65–2.47
(m, 2H), 2.22 (s, 3H), 2.04–1.96 (m, 1H), 1.72–1.61 (m, 1H);
13C{1H} NMR (101 MHz, CDCl3) δ 199.5, 144.1, 136.9,
135.6, 133.3, 132.6, 129.20, 129.15, 128.8, 127.6, 126.6, 49.5,
35.3, 28.6, 27.7, 21.1.
2-Methyl-1,3-diphenylpropan-1-one (8o).19 Yellow oil (71.8
mg, 80% yield); eluent DCM/PE (2/3) then DCM/PE (1/10);
1H NMR (400 MHz, CDCl3) δ 7.95–7.88 (m, 2H), 7.55–7.47
(m, 1H), 7.42 (t, J = 7.6 Hz, 2H), 7.29–7.12 (m, 5H), 3.76 –
3.71 (m, 1H), 3.19–3.13 (m, 1H), 2.71–2.65 (m, 1H), 1.19 (d,
J = 7.2 Hz, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ 203.8,
140.0, 136.5, 133.0, 129.1, 128.7, 128.4, 128.3, 126.2, 42.8,
39.4, 17.5.
2-(4-Bromobenzyl)-3,4-dihydronaphthalen-1(2H)-one
(8v).19 Yellow solid (104.6 mg, 83% yield); mp: 92−94 °C;
1
3-(2-Chlorophenyl)-2-methyl-1-phenylpropan-1-one (8p).
eluent DCM/PE (2/3); H NMR (400 MHz, CDCl3) δ 8.06–
1
Yellow oil (95.2 mg, 92% yield); eluent DCM/PE (1/4); H
8.04 (m, 1H), 7.50–7.35 (m, 3H), 7.31–7.28 (m, 1H), 7.20 (d,
J = 7.6 Hz, 1H), 7.10 (d, J = 8.0 Hz, 2H), 3.41–3.37 (m, 1H),
2.94–2.90 (m, 2H), 2.77–2.58 (m, 2H), 2.15–1.99 (m, 1H),
1.81–1.71 (m, 1H); 13C{1H} NMR (101 MHz, CDCl3) δ 199.0,
144.0, 139.1, 133.4, 132.4, 131.5, 131.1, 129.3, 128.8, 128.4,
127.6, 126.7, 120.0, 49.3, 35.2, 28.7, 27.8.
NMR (400 MHz, CDCl3) δ 8.00–7.84 (m, 2H), 7.57–7.47 (m,
1H), 7.42 (t, J = 7.6 Hz, 2H), 7.37–7.29 (m, 1H), 7.23–7.15
(m, 1H), 7.15–7.05 (m, 2H), 3.96–3.90 (m, 1H), 3.27–3.21 (m,
1H), 2.88–2.81 (m, 1H), 1.20 (d, J = 7.2 Hz, 3H); 13C{1H}
NMR (101 MHz, CDCl3) δ 203.7, 137.5, 136.5, 134.1, 133.0,
131.9, 129.5, 128.6, 128.3, 127.8, 126.7, 40.3, 37.3, 17.6; IR
(KBr pellet): ν 2972, 1679 (νc=o), 1596, 1474, 1447, 1288,
1052, 972, 750 cm−1; HRMS (ESI-TOF) m/z: [M + H]+ calcd
for C16H16ClO 259.0884, found 259.0890.
2-Benzyl-6-methoxy-3,4-dihydronaphthalen-1(2H)-one
(8w).37 Brown oil (95.8 mg, 90% yield); eluent DCM/PE (1/2);
1H NMR (400 MHz, CDCl3) δ 8.03 (d, J = 8.8 Hz, 1H), 7.32–
7.16 (m, 5H), 6.83–6.79 (m, 1H), 6.65 – 6.64 (m, 1H), 3.81 (s,
3H), 3.50–3.45 (m, 1H), 2.96–2.54 (m, 4H), 2.08–2.01 (m,
1H), 1.78–1.68 (m, 1H); 13C{1H} NMR (101 MHz, CDCl3) δ
198.1, 163.5, 146.5, 140.3, 130.0, 129.3, 128.4, 126.14,
126.12, 113.2, 1125, 55.4, 49.1, 35.8, 29.0, 27.7.
3-(Furan-2-yl)-2-methyl-1-phenylpropan-1-one (8q). Yel-
1
low oil (53.8 mg, 60% yield); eluent DCM/PE (2/3); H NMR
(400 MHz, CDCl3) δ 7.99−7.91 (m, 2H), 7.57−7.52 (m, 1H),
7.45 (t, J = 7.6 Hz, 1H), 7.29−7.27 (m, 1H), 6.25−6.22 (m,
1H), 6.05−5.96 (m, 1H), 3.89−3.83 (m, 1H), 3.17−3.11 (m,
1H), 2.79−2.13 (m, 1H), 1.22 (d, J = 7.2 Hz, 3H); 13C{1H}
NMR (101 MHz, CDCl3) δ 203.2, 153.7, 141.2, 136.2, 133.0,
128.7, 128.3, 110.2, 106.5, 40.0, 31.6, 17.5; IR (KBr pellet): ν
2972, 1678 (νc=o), 1596, 1581, 1448, 1222, 974, 793, 701 cm−1;
HRMS (ESI-TOF) m/z: [M + H]+ calcd for C14H15O2 215.1067,
found 215.1075.
2-(Furan-2-ylmethyl)-6-methoxy-3,4-dihydronaphthalen-
1(2H)-one (8x). Brown oil (64.6 mg, 63% yield); eluent
1
DCM/PE (1/10); H NMR (400 MHz, CDCl3) δ 8.02 (d, J =
8.4 Hz, 1H), 7.32–7.30 (m, 1H), 6.83–6.80 (m, 1H), 6.68–6.66
(m, 1H), 6.30–6.27 (m, 1H), 6.08–6.06 (m, 1H), 3.83 (s, 3H),
3.48–3.35 (m, 1H), 2.95–2.73 (m, 4H), 2.18–2.12 (m, 1H),
1.87–1.72 (m, 1H); 13C{1H} NMR (101 MHz, CDCl3) δ 197.6,
163.5, 154.1, 146.6, 141.2, 130.0, 126.0, 113.2, 112.5, 110.2,
106.6, 55.4, 46.9, 29.2, 28.3, 28.2; IR (KBr pellet): ν 2935,
1670 (νc=o), 1597, 1494, 1454, 1252, 1026, 793, 732 cm−1;
HRMS (ESI-TOF) m/z: [M + H]+ calcd for C16H17O3 257.1172,
found 257.1178.
2-Benzyl-6-methylcyclohexan-1-one (8r).19 Yellow oil (48.6
1
mg, 60% yield); eluent DCM/PE (2/3); H NMR (400 MHz,
CDCl3) δ 7.30–7.11 (m, 5H), 3.25–3.20 (m, 1H), 2.60–2.34
(m, 3H), 2.12–2.00 (m, 2H), 1.83–1.59 (m, 2H), 1.42–1.24 (m,
2H), 1.02 (d, J = 6.4 Hz, 3H); 13C{1H} NMR (101 MHz,
CDCl3) δ 213.7, 140.8, 129.2, 128.3, 125.9, 52.6, 45.7, 37.5,
35.6, 34.7, 25.5, 14.6.
2-Benzyl-2,3-dihydro-1H-inden-1-one (8y).4e Brown oil
1
(73.8 mg, 83% yield); eluent DCM/PE (2/3); H NMR (400
2-Benzyl-3,4-dihydronaphthalen-1(2H)-one (8s).30 Brown
oil (86.0 mg, 91% yield); eluent DCM/PE (2/3); 1H NMR (400
MHz, CDCl3) δ 8.08–8.04 (m, 1H), 7.45–7.40 (m, 1H), 7.34–
MHz, CDCl3) δ 7.76 (d, J = 7.6 Hz, 1H), 7.56–7.51 (m, 1H),
7.40–7.14 (m, 7H), 3.41–3.35 (m, 1H), 3.17–3.10 (m, 1H),
3.01–2.93 (m, 1H), 2.86–2.80 (m, 1H), 2.68–2.61 (m, 1H);
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13C{1H} NMR (101 MHz, CDCl3) δ 207.8, 153.7, 139.7,
136.6, 134.9, 128.9, 128.6, 127.5, 126.6, 126.4, 124.0, 49.0,
37.0, 32.2.
2-((1-Henzylpiperidin-4-yl)methyl)-5,6-dimethoxy-2,3-
dihydro-1H-inden-1-one (8ae).19 Brown oil (126.0 mg, 83%
1
2
1
yield); eluent DCM/PE (2/3); H NMR (400 MHz, CDCl3) δ
7.34–7.20 (m, 5H), 7.16 (s, 1H), 6.84 (s, 1H), 3.94 (s, 3H),
3.88 (s, 3H), 3.50 (s, 2H), 3.25–3.18 (m, 1H), 2.93–2.87 (m,
2H), 2.75–2.60 (m, 2H), 2.03–1.87 (m, 3H), 1.75–1.64 (m,
2H), 1.53–1.23 (m, 4H); 13C{1H} NMR (101 MHz, CDCl3) δ
207.7, 155.5, 149.4, 148.7, 138.3, 129.2, 128.1, 126.9, 107.4,
104.4, 63.4, 56.2, 56.0, 53.736, 53.722, 45.4, 38.7 34.4, 33.3,
33.0, 31.8.
3
4
5
6
7
8
9
2-Benzyl-5,6-dimethoxy-2,3-dihydro-1H-inden-1-one (8z).38
Yellow solid (110.6 mg, 98% yield); mp: 127−128 °C; eluent
1
DCM/PE (2/3); H NMR (400 MHz, CDCl3) δ 7.30–7.18 (m,
6H), 6.79 (s, 1H), 3.92–3.88 (m, 6H), 3.38–3.33 (m, 1H),
3.12–2.91 (m, 2H), 2.80–2.58 (m, 2H); 13C{1H} NMR (101
MHz, CDCl3) δ 206.4, 155.6, 149.5, 148.9, 139.8, 129.2,
128.9, 128.5, 126.3, 107.4, 104.4, 56.2, 56.0, 49.1, 37.2, 31.9.
General procedure for preparation of compound 9
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
5,6-Dimethoxy-2-(4-methylbenzyl)-2,3-dihydro-1H-inden-
To a 15 mL Schlenk flask was added ketone 3a (48.1 mg, 0.40
mmol), benzyl alcohol 4a (47.6 mg, 0.44 mmol), Ru complex
b (1.6 mg, 0.5 mol%) and K3PO4·3H2O (16.0 mg, 0.15 equiv) in
tamyl alcohol (0.5 mL) under an argon atmosphere. The reac-
1-one (8aa). Yellow solid (116.2 mg, 98% yield); mp:
1
110−111 °C; eluent EA/PE (1/1); H NMR (400 MHz, CDCl3)
δ 7.18 (s, 1H), 7.15–7.01 (m, 4H), 6.79 (s, 1H), 3.92 (s, 3H),
3.89 (s, 3H), 3.35–3.25 (m, 1H), 3.11–2.88 (m, 2H), 2.80–2.67
(m, 1H), 2.67–2.55 (m, 1H), 2.31 (s, 3H); 13C{1H} NMR (101
MHz, CDCl3) δ 206.5, 155.6, 149.4, 149.0, 136.7, 135.7,
129.3, 129.2, 128.8, 107.4, 104.4, 56.2, 56.1, 49.2, 36.8, 31.9,
21.0; IR (KBr pellet): ν 2924, 1678 (νc=o), 1591, 1500, 1453,
1260, 1118, 1013, 866, 838, 780 cm−1; HRMS (ESI-TOF) m/z:
[M + H]+ calcd for C19H21O3 297.1485, found 297.1495.
o
tion mixture was stirred at 120 C for 4 h, and then cooled to
room temperature. Next, p-methoxybenzyl alcohol 4b (60.8
mg, 0.44 mmol), Ru complex b (1.6 mg, 0.5 mol%) and
K3PO4·3H2O (53.3 mg, 0.50 equiv) was added, and the reaction
was continued for 12 h under an argon atmosphere. After the
reaction was completed, the reaction mixture was evaporated
and the residue was purified by TLC on silica gel plates using
DCM/PE (1/3) as eluent to afford the corresponding ketone
products 9 in 23% yield.
5,6-Dimethoxy-2-(4-(trifluoromethyl)benzyl)-2,3-dihydro-
1H-inden-1-one (8ab). Yellow solid (119.1 mg, 85% yield);
1
2-Benzyl-3-(4-methoxyphenyl)-1-phenylpropan-1-one (9).19
Yellow oil (30.7 mg, 23% yield); 1H NMR (400 MHz, CDCl3)
δ 7.78–7.76 (m, 2H), 7.48–7.41 (m, 1H), 7.33 (t, J = 7.6 Hz,
2H), 7.25–7.16 (m, 2H), 7.13 (d, J = 7.2 Hz, 3H), 7.05 (d, J =
8.4 Hz, 2H), 6.75 (d, J = 8.8 Hz, 2H), 4.03–3.91 (m, 1H), 3.73
(s, 3H), 3.14–3.04 (m, 2H), 2.83–2.70 (m, 2H); 13C{1H} NMR
(101 MHz, CDCl3) δ 203.5, 158.1, 139.6, 137.4, 132.8, 131.5,
130.0, 129.0, 128.5, 128.4, 128.1, 126.3, 113.8, 55.2, 50.7,
38.2, 37.4
mp: 126−128 °C; eluent EA/PE (1/1); H NMR (400 MHz,
CDCl3) δ 7.55 (d, J = 8.0 Hz, 2H), 7.36 (d, J = 8.0 Hz, 2H),
7.20 (s, 1H), 6.82 (s, 1H), 3.94 (s, 3H), 3.91 (s, 3H), 3.43–3.37
(m, 1H), 3.17–2.91 (m, 2H), 2.82–2.66 (m, 2H); 13C{1H}
NMR (101 MHz, CDCl3) δ 205.8, 155.8, 149.6, 148.7, 144.0,
129.2, 129.1, 128.7 (q, JC-F = 32.5 Hz), 125.4 (q, JC-F = 3.6
Hz), 124.3 (q, JC-F = 272.7 Hz), 107.4, 104.4, 56.2, 56.1, 48.7,
36.9, 31.7; 19F NMR (376 MHz, CDCl3) δ -62.37; IR (KBr
pellet): ν 2920, 1692 (νc=o), 1590, 1501, 1439, 1309, 1263,
1107, 1020, 837, 816, 735 cm−1; HRMS (ESI-TOF) m/z: [M +
H]+ calcd for C19H18F3O3 351.1203, found 351.1209.
ASSOCIATED CONTENT
Supporting Information
2-(Furan-2-ylmethyl)-5,6-dimethoxy-2,3-dihydro-1H-
inden-1-one (8ac). Brown solid (68.6 mg, 63% yield); mp:
120−121 °C; eluent DCM/PE (2/3); 1H NMR (400 MHz,
CDCl3) δ 7.30–7.28 (m, 1H), 7.19 (s, 1H), 6.84 (s, 1H), 6.29–
6.25 (m, 1H), 6.05–6.03 (m, 1H), 3.95 (s, 6H), 3.91 (s, 3H),
3.33–3.17 (m, 2H), 3.03−3.17 (m, 1H), 2.87−2.74 (m, 2H);
13C{1H} NMR (101 MHz, CDCl3) δ 205.9, 155.6, 153.7,
149.5, 149.0, 141.3, 129.1, 110.2, 107.4, 106.2, 104.4, 56.2,
56.1, 46.7, 32.2, 29.6; IR (KBr pellet): ν 2945, 1689 (νc=o),
1589, 1498, 1435, 1312, 1217, 1119, 1010, 863, 782, 729 cm−1;
HRMS (ESI-TOF) m/z: [M + H]+ calcd for C16H17O4 273.1121,
found 273.1131.
The Supporting Information is available free of charge on the
ACS Publications website.
Optimization of reaction conditions and spectra copies of pin-
cer precursors 2a−c, Ru(II) complexes a−c, and α-alkylation
products 5−6 and 8−9 (PDF)
AUTHOR INFORMATION
Corresponding Author
zhuxinju@zzu.edu.cn (X.Z); Shao_tian@zzu.edu.cn (T.S)
2-Hexyl-5,6-dimethoxy-2,3-dihydro-1H-inden-1-one (8ad).
Yellow solid (86.2 mg, 78% yield); mp: 206−208 °C; eluent
EA/PE (1/2); 1H NMR (400 MHz, CDCl3) δ 7.17 (s, 1H), 6.88
(s, 1H), 3.97 (s, 3H), 3.91 (s, 3H), 3.26–2.19 (m, 1H), 2.80–
2.59 (m, 2H), 1.98–1.91 (m, 1H), 1.46–1.27 (m, 8H), 0.88 (t, J
= 6.8 Hz, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ 207.7,
155.4, 149.3, 149.0, 129.5, 107.4, 104.3, 56.1, 56.0, 47.7,
32.6, 31.70, 31.67, 29.3, 27.3, 22.6, 14.0; IR (KBr pellet): ν
2925, 2857, 1680 (νc=o), 1592, 1500, 1453, 1262, 1218, 1104,
1033, 872, 835, 768 cm−1; HRMS (ESI-TOF) m/z: [M + H]+
calcd for C17H25O3 277.1798, found 277.1804.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
Financial support from the National Natural Science Founda-
tion of China (Grant Nos. 21528201 and 21672192), the China
Postdoctoral Science Foundation (Grant Nos. 2016M602254
and 2016M600582), and the Program for Science & Technol-
ogy Innovation Talents in Universities of Henan Province
(17HASTIT004) are gratefully appreciated.
REFERENCES
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Page 12 of 13
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